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

Abstract

To provide a curable composition having superior adhesion and film durability, while maintaining superior developability and line width stability even after storage.SOLUTION: The above 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) includes a multifunctional urethane (meth)acrylate (B1) having a secondary or tertiary amine structure. The thermally crosslinkable compound (D) includes a compound (D1) having a blocked isocyanate group.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a curable composition used for forming an optical filter or the like.

Background Art

[0002] A color filter, which is a type of optical filter used in an image display device, a solid-state imaging device, etc., can be manufactured, for example, through the following steps. A step of applying a curable composition to a substrate such as glass (hereinafter referred to as the coating step), a step of removing the solvent from the coating film by drying (hereinafter referred to as the drying step), a step of irradiating and curing the coating film with ultraviolet rays through a photomask having a desired pattern shape (hereinafter referred to as the exposure step), then, a step of washing and removing the unexposed portion of the coating film with a developer (hereinafter referred to as the development step), and thereafter, a step of performing heat treatment to sufficiently cure the film (hereinafter referred to as the post-bake step) to obtain the pattern of the first color. Then, if necessary, by using curable compositions of different colors and performing the same operations, patterns of the second color and subsequent colors are sequentially formed to manufacture a color filter.

[0003] In recent years, due to the miniaturization and high pixel density of image display devices and solid-state imaging devices, the pattern has become finer and the difficulty of formation has increased. Also, in order to improve the productivity of color filters, it is required to reduce the integrated exposure amount required for pattern formation and to lower the heating temperature in order to reduce the environmental load. Therefore, the adhesion of the pattern and the resistance of the film have become problems. Furthermore, when the curable composition is stored, there is also a problem that the development time and the width of the pattern change compared to before storage.

[0004] To solve the above problems, for example, Patent Document 1 discloses a photosensitive colored resin composition capable of suppressing the generation of development residues and forming a colored layer with a good pattern shape even by low-temperature heat treatment. The composition contains a colorant, an alkali-soluble resin, a non-reactive resin, a photopolymerizable compound, a photoinitiator, and a solvent. The alkali-soluble resin has an acid value exceeding 50 mgKOH / g, the non-reactive resin has an acid value of 7 mgKOH / g to 50 mgKOH / g, the content of structural units derived from methyl methacrylate is 50% to 99% by mass in all structural units, and the weight average molecular weight is 5000 to 50000. Patent Document 2 discloses a photosensitive resin composition capable of realizing a highly sensitive photocured pattern while having excellent substrate adhesion and residual film ratio. The composition contains an alkali-soluble resin, a polymerizable compound, a photopolymerization initiator, and a solvent, and the photopolymerization initiator contains a compound with a specific structure. Patent Document 3 discloses a curable resin composition capable of providing a cured product having sufficient surface hardness and excellent electrical properties. The composition 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.

Prior Art Documents

Patent Documents

[0005]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0006] However, the compositions described in Patent Documents 1 to 3 had insufficient adhesion and film resistance. Further, the developability and pattern width after storing the composition were not considered.

[0007] An object of the present invention is to provide a curable composition having excellent adhesion and film resistance, and excellent developability and line width stability even after storage.

Means for Solving the Problems

[0008] The present invention is a curable composition containing an alkali-soluble resin (A), a polymerizable compound (B), a polymerization initiator (C), and a thermally crosslinkable compound (D), wherein the polymerizable compound (B) contains a polyfunctional urethane (meth) acrylate (B1) having a secondary amine or tertiary amine structure, and the thermally crosslinkable compound (D) relates to a curable composition containing a compound (D1) having a blocked isocyanate group.

Effects of the Invention

[0009] According to the present invention described above, a curable composition having excellent adhesion and film resistance, and excellent developability and line width stability even after storage can be provided. Further, the present invention can provide a film, an optical filter, a solid-state imaging device, an image display device, and an infrared sensor using the same. Note that the film resistance is solvent resistance.

Brief Description of the Drawings

[0010]

Figure 1

Modes for Carrying Out the Invention

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

[0012] In this specification, unless otherwise specified, “(meth)acryloyl”, “(meth)acrylic”, “(meth)acrylic acid”, “(meth)acrylate”, or “(meth)acrylamide” means “acryloyl and / or methacryloyl”, “acrylic and / or methacrylic”, “acrylic acid and / or methacrylic acid”, “acrylate and / or methacrylate”, or “acrylamide and / or methacrylamide”, respectively. Also, “C.I.” means Color Index (C.I.; published by The Society of Dyers and Colourists). In this specification, the polymerizable unsaturated group is an ethylenically unsaturated double bond. 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 a state in which the monomer forms a resin after polymerization. In this specification, a low-molecular compound whose molecular weight can be specified is a value calculated by calculation (formula weight) or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry). For a compound having a molecular weight distribution, it is the polystyrene-converted weight-average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent. In this specification, a numerical range represented by “~” means a range including the numerical values described before and after “~” as the lower limit value and the upper limit value.

[0013] <Curable composition> A curable composition according to an embodiment of the present invention is a curable composition containing an alkali-soluble resin (A), a polymerizable compound (B), a polymerization initiator (C), and a thermally crosslinkable compound (D), wherein the polymerizable compound (B) contains a polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure, and the thermally crosslinkable compound (D) contains a compound (D1) having a blocked isocyanate group.

[0014] Although the mechanism by which the curable composition having the above configuration can solve the problems of the present invention is not clear, it is presumed as follows.

[0015] In the curable composition, the polymerization initiator is decomposed by light or heat to generate active species. These active species add to the polymerizable compound to newly generate active species, which proceed chainwise to polymerize. However, if these active species are inactivated by external factors, the polymerization reaction stops. When the active species are radicals, oxygen inhibits the polymerization (also called oxygen inhibition). Since oxygen is in the triplet state in the ground state, it has high reactivity with radicals and easily reacts with radical active species to form peroxy radicals. Since these peroxy radicals have poor reactivity with the polymerizable compound, the progress of the polymerization reaction is inhibited. Therefore, when the integrated exposure amount is small, the adhesion and film resistance are likely to deteriorate. Usually, since optical filters such as color filters are manufactured in an air atmosphere, they are subject to polymerization inhibition by oxygen in the exposure process and the polymerization does not proceed sufficiently, but the polymerization is promoted by heat treatment at a high temperature thereafter. Therefore, in the case of heat treatment at a low temperature, the film resistance is likely to deteriorate due to insufficient curing. The polyfunctional urethane (meth)acrylate (B1) having a secondary or tertiary amine structure is presumed to easily generate a carbon radical by having a secondary or tertiary amine structure in the molecule due to hydrogen being abstracted. Therefore, the generated peroxy radical abstracts hydrogen from the polyfunctional urethane (meth)acrylate (B1) having a secondary or tertiary amine structure, and the newly generated carbon radical initiates polymerization. In addition, since the generated carbon radical can capture oxygen, it also has the effect of reducing the oxygen concentration at the polymerization site. Due to these mechanisms, it is presumed that polymerization inhibition by oxygen is suppressed and polymerization proceeds sufficiently, thereby improving adhesion and film resistance. Furthermore, the polyfunctional urethane (meth)acrylate (B1) having a secondary or tertiary amine structure forms a physical crosslinked structure by intermolecular hydrogen bonding between urethane bonds or between functional groups of the substrate together with a chemical crosslinked structure by polymerization. The molecular cohesive energy of the intermolecular hydrogen bond at this urethane bond part is larger than the cohesive energy of other organic structures such as ether bonds. Therefore, it is presumed that the film becomes stronger due to the interaction between urethane bonds, and adhesion and film resistance are improved. And the isocyanate group of the compound (D1) having a blocked isocyanate group used in combination is protected by a blocking agent, so it is difficult to react with other components during storage, and development properties and changes in line width are also suppressed when used after a lapse of time. And it is presumed that the film resistance is further improved when the isocyanate group from which the blocking agent has desorbed by heating during post-baking reacts with other components, or the blocking agent does not desorb and transesterifies with other components.

[0016] Hereinafter, the components contained in or that can be contained in the curable composition of one embodiment will be described in detail.

[0017] [Alkali-soluble resin (A)] The curable composition of the present invention contains an alkali-soluble resin (A).

[0018] The alkali-soluble resin (A) only needs to be soluble in the alkali developer described later and is not particularly limited, and known resins can be used. Examples of the resin type of the alkali-soluble resin (A) include (meth)acrylic resins, styrene resins, styrene / (meth)acrylic resins, epoxy resins, urethane resins, polycarbonate resins, polyester resins, polyether resins, polyimide resins, polyamideimide resins, cyclic olefin resins, polysiloxane resins, and the like.

[0019] The alkali-soluble resin (A) preferably has an alkali-soluble group. Examples of the alkali-soluble group include acidic groups such as carboxyl groups, phosphate groups, and sulfonic acid groups. Among these, from the viewpoint of developability, carboxyl groups are more preferable.

[0020] Examples of the structure of the alkali-soluble resin (A) include a chain random structure, a chain block structure, a graft structure, a comb structure, and a star structure. Among these, from the viewpoint of film resistance, a chain random structure is preferable.

[0021] 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.

[0022] The acid value of the alkali-soluble resin (A) is preferably 30 to 200 mgKOH / g, and more preferably 40 to 180 mgKOH / g.

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

[0024] The alkali-soluble resin (A) is preferably 1 to 95% by mass, and more preferably 3 to 80% by mass, based on 100% by mass of the non-volatile content of the curable composition.

[0025] (Alkali-soluble resin (A1) having a hydroxyl group-containing monomer unit (a1)) From the perspective of film resistance, the alkali-soluble resin (A) preferably contains an alkali-soluble resin (A1) having a hydroxyl group-containing monomer unit (a1) (hereinafter, also simply referred to as the alkali-soluble resin (A1)). It is presumed that the film resistance is improved because the hydroxyl group of the alkali-soluble resin (A1) reacts with the compound (D1) having a blocked isocyanate group in the post-baking process.

[0026] The alkali-soluble resin (A1) is not particularly limited as long as it is an alkali-soluble resin having a hydroxyl group, and can be produced by a known method. For example, it can be produced by the following methods (i) to (iii), etc. Note that the present invention is not limited thereto.

[0027] <Method (i)> Method (i) of copolymerizing a hydroxyl group-containing monomer that forms a hydroxyl group-containing monomer unit (a1) and a monomer that can be copolymerized with it optionally.

[0028] 〔Hydroxyl group-containing monomer unit (a1)〕 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.

[0029] Examples of the monomer copolymerizable with the hydroxyl group-containing monomer include the monomers that form the monomer units (a2) to (a8) described later.

[0030] <Method (ii)> Method (ii) of introducing a hydroxyl group by adding a compound (modifying compound) having a carboxyl group to the epoxy group contained in the resin (precursor).

[0031] <Method (iii)> Method (iii) of introducing a hydroxyl group by adding a compound having an epoxy group (modifying compound) to the carboxyl group contained in the resin (precursor).

[0032] From the viewpoints of film resistance, developability after storage, and line width stability after storage, the content of the hydroxyl group-containing monomer unit (a1) is preferably 1 to 60 mol%, more preferably 5 to 50 mol% in all the constituent units of the alkali-soluble resin (A1).

[0033] The alkali-soluble resin (A1) can 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 polycyclic alicyclic hydrocarbon group-containing monomer units (a2), acidic group-containing monomer units (a3), epoxy group-containing monomer units (a4), polymerizable unsaturated group-containing monomer units (a5), aromatic ring-containing monomer units (a6), blocked isocyanate group-containing monomer units (a7), and other monomer units (a8). Among these, from the viewpoint of film resistance, the alkali-soluble resin (A1) preferably has polycyclic alicyclic hydrocarbon group-containing monomer units (a2), and from the viewpoint of developability, acidic group-containing monomer units (a3).

[0034] 〔Polycyclic alicyclic hydrocarbon group-containing monomer unit (a2)〕 Monomers that form the polycyclic alicyclic hydrocarbon group-containing monomer unit (a2) include, for example, isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, adamantyl (meth)acrylate, and the like. 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.

[0035] The content of the monomer unit (a2) containing a polycyclic alicyclic hydrocarbon group is preferably 1 to 60 mol%, more preferably 3 to 40 mol%, in all the constituent units of the alkali-soluble resin (A1).

[0036] Monomer unit (a3) containing an acidic group Examples of the acidic group-containing monomer include (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl hexylhydrophthalic acid, p-styrenesulfonic acid, vinylsulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, 2-(meth)acryloyloxyethyl acid phosphate, and the like. These monomers can be used alone or in combination of two or more.

[0037] From the viewpoint of developability, the content of the monomer unit (a3) containing an acidic group is preferably 1 to 60 mol%, more preferably 5 to 50 mol%, in all the constituent units of the alkali-soluble resin (A1).

[0038] As a method for introducing the monomer unit (a3) containing an acidic group into the alkali-soluble resin (A1), in addition to the method of copolymerizing a hydroxyl group-containing monomer and an acidic group-containing monomer, a method of adding an acid anhydride (modifying compound) to the hydroxyl group of the alkali-soluble resin (A1) may be used. Examples of the acid anhydride include succinic anhydride, phthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, and the like.

[0039] Monomer unit (a4) containing an epoxy group The epoxy group-containing monomer is, for example, oxiranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxiranylethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate, and the like. These monomers can be used alone or in combination of two or more.

[0040] [Polymerizable unsaturated group-containing monomer unit (a5)] Examples of the method for incorporating the polymerizable unsaturated group-containing monomer unit (a5) into the alkali-soluble resin (A1) include the following methods (iv) to (vi).

[0041] [Method (iv)] In method (iv), for example, first, a precursor having an epoxy group-containing monomer unit (a4) is synthesized. Next, a monomer having a carboxyl group (modifying compound) among the above-mentioned acidic group-containing monomers is added to the epoxy group of the precursor.

[0042] [Method (v)] In method (v), for example, first, a precursor having an acidic group-containing monomer unit (a3) whose acidic group is a carboxyl group is synthesized. Next, the above-mentioned epoxy group-containing monomer (modifying compound) is added to the carboxyl group of the precursor.

[0043] Furthermore, an acid anhydride (modifying compound) can be further reacted with the hydroxyl group generated by the reactions of methods (iv) and (v) to incorporate an acidic group.

[0044] Examples of the acid anhydride include 1,2,3,6-tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like.

[0045] <Method (vi)> In method (vi), for example, first, a precursor having a hydroxyl group-containing monomer (a1) is synthesized. Then, the isocyanate group of an isocyanate group-containing monomer (modified compound) is reacted with the hydroxyl group of the precursor.

[0046] Examples of the isocyanate group-containing monomer 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.

[0047] [Aromatic ring-containing monomer unit (a6)] Examples of the aromatic ring-containing monomer include styrene, α-methylstyrene, vinylnaphthalene, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, para-cumylphenol ethylene oxide (EO) or propylene oxide (PO) modified (meth)acrylate, phenol EO or PO modified (meth)acrylate, nonylphenol EO or PO modified (meth)acrylate, N-phenylmaleimide, N-benzylmaleimide, and the like. These monomers can be used alone or in combination of two or more.

[0048] [Block isocyanate group-containing monomer unit (a7)] The block isocyanate group-containing monomer is a monomer in which the isocyanate group of an isocyanate group-containing monomer is protected with a compound (hereinafter also referred to as a blocking agent) that desorbs by heat. The desorption temperature of the blocking agent is preferably 60 to 160°C.

[0049] Isocyanate group-containing monomers include, for example, 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, and the like. Further, an equimolar reaction product of 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used.

[0050] Blocking agents include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds, and the like.

[0051] Examples of oxime compounds include formaldehyde oxime, acetaldehyde oxime, acetone oxime, methyl ethyl ketone oxime, methyl isobutyl ketone oxime, cyclohexanone oxime, benzophenone oxime, and the like. Among these, methyl ethyl ketone oxime is preferred. Examples of lactam compounds include ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam, and the like. Examples of phenol compounds include phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, p-nitrophenol, and the like. Among these, 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferred. Examples of alcohol compounds include methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol. Examples of the amine compound include diphenylamine, phenylnaphthylamine, aniline, carbazole, and the like. 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., and diethyl malonate is preferred. Examples of the pyrazole compound include pyrazole, methylpyrazole, 3,5-dimethylpyrazole, etc., and 3,5-dimethylpyrazole is preferred. Examples of the mercaptan compound include butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc. Examples of the imidazole compound include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1-benzyl-2-phenylimidazole, etc. Examples of the imide compound include succinimide, maleimide, maleic imide, phthalimide, etc. Examples of the urea compound include urea, thiourea, ethylene urea, etc. Examples of the imine compound include ethyleneimine, polyethyleneimine, etc. Examples of the bisulfite compound include sodium bisulfite, potassium bisulfite, etc.

[0052] The blocking agent can be used alone or in combination of two or more.

[0053] Preferably, the blocking agent is at least one selected from the group consisting of an oxime compound, a lactam compound, a phenol compound, an alcohol compound, an amine compound, an active methylene compound, a pyrazole compound, a mercaptan compound, an imidazole compound, and an imide compound. From the viewpoints of the protection reaction and the deprotection reaction, more preferably, the blocking agent is at least one selected from the group consisting of an oxime compound, a phenol compound, an active methylene compound, and a pyrazole compound.

[0054] Examples of the block isocyanate group-containing monomer include, but are not limited to, the following compounds.

[0055] [Chemical formula]

[0056] Commercially available block isocyanate group-containing monomers include, for example, Calenz MOI-DEM (blocking agent desorption temperature: 85 - 95°C), MOI-BP (blocking agent desorption temperature: 105 - 115°C), MOI-BM (blocking agent desorption temperature: 125 - 135°C), etc. manufactured by Resonaak. These monomers can be used alone or in combination of two or more.

[0057] When the polymerization initiator (C) described later contains only the photopolymerization initiator (C1), the alkali-soluble resin (A1) preferably has a block isocyanate group-containing monomer unit (a7) from the viewpoint of film resistance. The isocyanate group from which the blocking agent has desorbed by heat treatment reacts with the hydroxyl group or other components of the alkali-soluble resin (A1). Alternatively, the blocking agent does not desorb and reacts with the hydroxyl group of the alkali-soluble resin (A1) by transesterification. It is presumed that the film resistance is thereby improved.

[0058] From the viewpoint of film resistance, the content of the block isocyanate group-containing monomer unit (a7) is preferably 1 to 50 mol%, more preferably 3 to 40 mol% in all the constituent units of the alkali-soluble resin (A1).

[0059] [Other monomer unit (a8)] Other monomers include, for example, acrylic 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, diethylaminoethyl (meth)acrylate, etc.; (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, etc.; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, etc.; Vinyl fatty acids such as vinyl acetate or vinyl propionate, etc.; N-substituted maleimides such as methyl maleimide, ethyl maleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, etc.; Examples include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, etc. These monomers can be used alone or in combination of two or more.

[0060] The weight average molecular weight of the alkali-soluble resin (A1) is preferably from 3,000 to 50,000, more preferably from 4,000 to 40,000.

[0061] The molecular weight distribution (weight average molecular weight / number average molecular weight) of the alkali-soluble resin (A1) is preferably from 1.2 to 3.0, more preferably from 1.3 to 2.8.

[0062] The acid value of the alkali-soluble resin (A1) is preferably from 20 to 200 mgKOH / g, more preferably from 30 to 180 mgKOH / g.

[0063] The alkali-soluble resin (A1) can be used alone or in combination of two or more.

[0064] The content of the alkali-soluble resin (A1) is preferably from 10 to 100% by mass, more preferably from 20 to 100% by mass, based on 100% by mass of the alkali-soluble resin (A).

[0065] (Alkali-soluble resin (A2) other than the alkali-soluble resin (A1)) The alkali-soluble resin (A) can contain an alkali-soluble resin (A2) other than the alkali-soluble resin (A1) (hereinafter, also simply referred to as the other alkali-soluble resin (A2)).

[0066] [Polymerizable compound (B)] The curable composition of the present invention contains a polymerizable compound (B).

[0067] The polymerizable compound (B) is not particularly limited as long as it is polymerizable, and known polymerizable compounds can be used. For example, monomers, oligomers, etc. having a polymerizable unsaturated group can be mentioned. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a (meth)acryloyloxy group, a styryl group, etc.

[0068] The polymerizable compound (B) can be used alone or in combination of two or more.

[0069] The content of the polymerizable compound (B) is preferably from 1 to 80% by mass, more preferably from 5 to 70% by mass, based on 100% by mass of the non-volatile content of the curable composition.

[0070] (Polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure) The polymerizable compound (B) contains polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure.

[0071] Note that the amine structure of the polyfunctional urethane (meth)acrylate (B1) having a secondary amine or 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.

[0072] The number of (meth)acryloyl groups of the polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure is preferably 2 to 60.

[0073] The weight average molecular weight of the polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure is preferably 500 to 50,000, more preferably 1,000 to 30,000.

[0074] The molecular weight distribution (weight average molecular weight / number average molecular weight) of the polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure is preferably 1.5 to 5.0.

[0075] The acid value of the polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure is preferably 10 mgKOH / g or less.

[0076] The polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure can be used alone or in combination of two or more.

[0077] The content of the polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure is preferably 0.1 to 80% by mass, more preferably 0.5 to 60% by mass in 100% by mass of the polymerizable compound (B).

[0078] The polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure can be synthesized as follows. 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 with a polyisocyanate compound (Z).

[0079] Examples of the (meth)acrylate compound (X) include ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolpropane EO or PO modified tri(meth)acrylate, ditrimethylolpropane EO or PO modified tetra(meth)acrylate, pentaerythritol EO or PO modified tetra(meth)acrylate, dipentaerythritol EO or PO modified hexa(meth)acrylate, etc.

[0080] The (meth)acrylate compound (X) can be used alone or in combination of two or more.

[0081] 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.

[0082] The amine compound (Y) having a hydroxyl group can be used alone or in combination of two or more thereof.

[0083] The method for the Michael addition reaction between 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 mentioned.

[0084] The polyisocyanate compound (Z) is, for example, a polyisocyanate compound having an aliphatic structure such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, 2,2,4-trimethylhexamethylene diisocyanate; a polyisocyanate compound 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; Polyisocyanate compounds having an aromatic structure such as 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bis(chloromethyl)diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, bis(isocyanatomethyl)benzene, etc. can be mentioned. In addition, these burette bodies, isocyanurate bodies, adduct bodies, allophanate bodies, etc. can be mentioned.

[0085] The polyisocyanate compound (Z) can be used alone or in combination of two or more.

[0086] The method of the urethane reaction between the precursor and the polyisocyanate compound (Z) is not particularly limited, and known methods can be used. For example, the methods described in Japanese Patent Application Laid-Open No. 2018-517797, etc. can be mentioned.

[0087] The polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure is more preferably one or more selected from the group consisting of an aliphatic polyfunctional urethane (meth)acrylate having a secondary amine or tertiary amine structure and an alicyclic polyfunctional urethane (meth)acrylate having a secondary amine or tertiary amine structure from the viewpoint of adhesion.

[0088] The aliphatic polyfunctional urethane (meth)acrylate having a secondary amine or tertiary amine structure can be obtained by using the polyisocyanate compound having the aliphatic structure as the above-mentioned polyisocyanate compound (Z).

[0089] The alicyclic polyfunctional urethane (meth)acrylate having a secondary amine or tertiary amine structure can be obtained by using the polyisocyanate compound having an alicyclic structure as the above-described polyisocyanate compound (Z).

[0090] Commercially available products of the polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure include, for example, CN9906NS of an aliphatic polyfunctional urethane acrylate having a tertiary amine structure manufactured by Arkema.

[0091] ((Meth)acrylate (B2) other than the polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure) From the viewpoints of film resistance, developability after storage, and line width stability after storage, the polymerizable compound (B) preferably contains a (meth)acrylate (B2) other than the polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure (hereinafter, also simply referred to as other (meth)acrylate (B2)).

[0092] Other (meth)acrylate (B2) can be used alone or in combination of two or more.

[0093] The content of other (meth)acrylate (B2) is preferably 20 to 99.9% by mass in 100% by mass of the polymerizable compound (B).

[0094] From the viewpoints of film resistance, developability after storage, and line width stability after storage, other (meth)acrylate (B2) preferably contains one or more selected from the group consisting of bifunctional (meth)acrylate and trifunctional (meth)acrylate.

[0095] [Bifunctional (meth)acrylate] The bifunctional (meth)acrylate includes, for example, 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, neopentyl glycol hydroxypivalate di(meth)acrylate, 2-hydroxy-3-methacryloylpropyl acrylate, 1,3-butylene glycol 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, tricyclodecanedimethanol 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 and the like can be mentioned.,

[0096] Examples of commercially available difunctional (meth)acrylates include 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 Specialyt 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 manufactured by Kyoeisha Chemical Co., Ltd.; Epoxy Ester 40EM, 70PA, 200PA, 80MFA; 3002M(N), 3000MK, 3000A; KAYARAD R-167, HX-220, HX-620, R-604 manufactured by Nippon Kayaku Co., Ltd. and the like.,

[0097] From the viewpoint of line width stability in pattern formation after storage, the difunctional (meth)acrylate preferably contains a compound represented by the following general formula (1).

[0098] General formula (1)

Chemical formula

[0099] 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 from 0 to 10, and n represents an integer from 6 to 20.

[0100] From the perspective of reactivity, R1 and R2 are preferably hydrogen atoms.

[0101] The number of carbon atoms of the alkylene group represented by A1 and A2 is preferably 1 to 5, more preferably 1 to 4, and particularly preferably 2 or 3. The alkylene group may be either linear or branched. Specific examples of the alkylene group include an ethylene group, a linear or branched propylene group, and the like.

[0102] From the perspective of line width stability after storage, l and m are preferably 0 to 5, and more preferably 0 to 3.

[0103] From the perspective of line width stability after storage, n is preferably 6 to 12, and more preferably 6 to 10.

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

[0105] The content of the bifunctional (meth)acrylate is preferably 0.1 to 20% by mass, and more preferably 0.1 to 10% by mass, in 100% by mass of the other (meth)acrylate (B2).

[0106] 〔Trifunctional (meth)acrylate〕 The trifunctional (meth)acrylate includes, for example, 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, caprolactone-modified trimethylolpropane tri(meth)acrylate, and the like.

[0107] Commercially available trifunctional (meth)acrylates include, for example, 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., and the like.

[0108] From the viewpoint of film resistance, the trifunctional (meth)acrylate preferably contains a trifunctional (meth)acrylate having a hydroxyl group. Further, from the viewpoint of developability after storage, the trifunctional (meth)acrylate preferably contains a trifunctional (meth)acrylate having an acidic group.

[0109] The trifunctional (meth)acrylate can be used alone or in combination of two or more.

[0110] The content of the trifunctional (meth)acrylate is preferably 5 to 99% by mass, more preferably 10 to 99% by mass, in 100% by mass of the other (meth)acrylate (B2).

[0111] Other (meth)acrylates (B2) can include those other than bifunctional (meth)acrylates and trifunctional (meth)acrylates. For example, 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, ditrimethylolpropane 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 and the like can be mentioned., Commercially available products include, for example, Light Esters HOA(N), HOP-A(N), HOB(N) manufactured by Kyoeisha Chemical Co., Ltd., Light Acrylate HOB-A, Epoxy Ester M-600A, HOA-MPE(N), UA-306H, UA-306T, UA-306I, UA-510H manufactured by NOF Corporation, Brenmer GLM, GLM-EX, GLM-R, G-FA80, PE-90, PE-200, PP-500, 50PEP-300 manufactured by Nippon Oil & Fats Co., Ltd., 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., Biscoat #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, Inc., Etercure 6361-100, 6362-100, 6363, DR-E522 manufactured by Eternal Materials Co., Ltd., etc.

[0112] [Polymerization initiator (C)] The curable composition of the present invention contains a polymerization initiator (C).

[0113] The polymerization initiator (C) is not particularly limited, and known polymerization initiators can be used. For example, compounds that generate radicals by the action of light or heat to initiate or accelerate radical polymerization reactions can be mentioned. The polymerization initiator (C1) that generates radicals by light (hereinafter also simply referred to as the photoinitiator (C1)) is preferably a compound that generates radicals with respect to light rays in the ultraviolet to visible region. The polymerization initiator (C2) that generates radicals by heat (hereinafter also simply referred to as the thermal polymerization initiator (C2)) may be a compound that generates radicals by the action of heat and light.

[0114] (Photoinitiator (C1)) Examples of the photoinitiator (C1) include α-hydroxy ketone compounds such as 1-hydroxycyclohexyl phenyl ketone, 2-hydroxy-2-methylpropiophenone, 2-hydroxy-1-[4-(2-hydroxyethoxy)phenyl]-2-methyl-1-propanone; 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; acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, diphenyl-2,4,6-trimethylbenzoylphosphine oxide; oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetoxyoxime); 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; Examples include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone.

[0115] Commercially available products include, as α-hydroxyketone compounds, Omnirad 127, 184, 1173, 2959 manufactured by IGM Resins; as α-aminoketone compounds, Omnirad 907, 369E, 379EG manufactured by IGM Resins; as acylphosphine compounds, Omnirad 819, TPO manufactured by IGM Resins; as oxime compounds, IRGACURE OXE-01, 02, 03, 04, 05 manufactured by BASF Japan, Adeka Arcles N-1919T, NCI-730, 831E, 930 manufactured by ADEKA, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, 3057 manufactured by Changzhou Strong New Materials Co., Ltd., Omnirad 1312, 1314, 1316 manufactured by IGM Resins, SPI-02, 03, 04, 05, 06, 07 manufactured by Samyang Corporation, DFI-020, 306, EOX-01 manufactured by Daito Chemicals, etc. In addition, compounds described in JP-A Nos. 2007-210991, 2009-179619, 2010-037223, 2010-215575, 2011-020998, WO 2015 / 036910, JP-T No. 2019-507108, JP-T No. 2019-528331, WO 2021 / 175855, JP-T No. 2022-5115524, etc. are also included.

[0116] From the viewpoints of adhesion and film resistance, the photopolymerization initiator (C1) preferably contains an oxime-based compound. From the viewpoints of adhesion and film resistance, the oxime-based compound has a molar absorptivity of light with a wavelength of 365 nm in propylene glycol monomethyl ether acetate of 5.0×10 3 An oxime-based compound of L / mol·cm or more is more preferable.

[0117] (Thermal polymerization initiator (C2)) Examples of the thermal polymerization initiator (C2) include pinacol-based compounds such as benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tert-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2-tetraphenylethane; Azobis 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. can be mentioned. In addition, oxime sulfonate compounds described in International Publication No. 2012 / 101245, International Publication No. 2016 / 030790, etc. can be mentioned.

[0118] From the viewpoints of film resistance, developability after storage, and line width stability after storage, the thermal polymerization initiator (C2) preferably has a 10-hour half-life temperature of 70 to 130°C, more preferably 80 to 120°C. Specifically, 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-hexylperoxyisopropyl monocarbonate (95°C), tert-butylperoxy-2-ethylhexyl monocarbonate (99°C), tert-butylperoxyacetate (101.9°C), butyl 4,4-bis[(tert-butyl)peroxy]pentanoate (104.5°C), di-tert-hexyl peroxide (116.4°C), di(2-tert-butylperoxyisopropyl)benzene (119.2°C), etc. may be mentioned. The values in parentheses are the 10-hour half-life temperatures.

[0119] The polymerization initiator (C) can be used alone or in combination of two or more.

[0120] The content of the polymerization initiator (C) is preferably 0.1 to 20% by mass, more preferably 0.5 to 10% by mass, based on 100% by mass of the non-volatile content of the curable composition.

[0121] From the viewpoint of film resistance, it is preferable to use the photopolymerization initiator (C1) and the thermal polymerization initiator (C2) in combination. By performing the radical polymerization reaction in both the exposure step and the post-bake step, the film resistance is further improved.

[0122] 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.

[0123] [Thermally crosslinkable compound (D)] The curable composition of the present invention contains a thermally crosslinkable compound (D). Note that the thermally crosslinkable compound (D) does not have an alkali-soluble group.

[0124] The thermally crosslinkable compound (D) is not particularly limited as long as it is a compound having a thermally crosslinkable group, and known compounds can be used. For example, compounds having an epoxy group, compounds having a blocked isocyanate group, compounds having an oxetanyl group, compounds having a methylol group, compounds having a phenol group, etc. can be mentioned.

[0125] The thermally crosslinkable compound (D) can be used alone or in combination of two or more.

[0126] The content of the thermally crosslinkable compound (D) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, in 100% by mass of the non-volatile content of the curable composition.

[0127] (Compound (D1) having a blocked isocyanate group) The thermally crosslinkable compound (D) includes a compound (D1) having a blocked isocyanate group.

[0128] 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 with a blocking agent. The elimination temperature of the blocking agent for the blocked isocyanate group is preferably 60 to 160°C, more preferably 70 to 130°C or lower.

[0129] 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. For example, the methods described in JP-A-52-116420, JP-A-60-149572, JP-A-7-31953, JP-A-10-306136, JP-A-2012-012567, etc. can be mentioned.

[0130] The blocking agents include the compounds described above. Among these, at least one selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds is preferable, and at least one selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds is more preferable. From the viewpoints of film resistance, developability after storage, and line width stability after storage, active methylene compounds are particularly preferable. Since the elimination temperature of the active methylene compound or the temperature of the transesterification reaction is 80 to 110°C, no reaction occurs during storage, and developability and line width stability after storage can be maintained. Thereby, the film resistance is improved by reacting in the post-bake step.

[0131] Compounds having an isocyanate group include, for example, compounds having an aliphatic structure such as butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene 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-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bis(chloromethyl)diphenylmethane diisocyanate, 2,6-diisocyanate-benzyl chloride, bis(isocyanatemethyl)benzene, etc. are included. In addition, burette forms, isocyanurate forms, adduct forms, allophanate forms of these compounds, and reaction products of these compounds and polyols, etc. are included.

[0132] From the viewpoint of adhesion, compounds having an isocyanate group, burette forms, isocyanurate forms, adduct forms, allophanate forms of compounds having an aliphatic structure or compounds having an alicyclic structure are preferable.

[0133] 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. Note that the present invention is not limited to these.

[0134]

Chemical formula

[0135] Examples of the X (blocked isocyanate group) of the above compounds include the structures represented by the following (X-1) to (X-6). In the following structures, * represents a bonding part. Note that the present invention is not limited to these.

[0136]

Chemical formula

[0137] Commercially available compounds having a blocked isocyanate group (D1) and having an aliphatic structure include, for example, 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, etc. manufactured by Baxenden Chemical Co., Ltd.; Compounds having an alicyclic structure include, for example, Takenate B-846N manufactured by Mitsui Chemicals, Inc.; Coronate BI-301, 2507, 2554 manufactured by Tosoh Corporation; BI7950, BI7951, BI7990, etc. manufactured by Baxenden Chemical Co., Ltd.; Compounds having an aromatic structure include, for example, Takenate B-830, B-815N, etc. manufactured by Mitsui Chemicals, Inc.

[0138] 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.

[0139] 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.

[0140] The acid value of the compound (D1) having a blocked isocyanate group is preferably 10 mgKOH / g or less.

[0141] The compound (D1) having a blocked isocyanate group can be used alone or in combination of two or more.

[0142] The content of the compound (D1) having a blocked isocyanate group is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, in 100% by mass of the non-volatile content of the curable composition.

[0143] (Compound (D2) having an epoxy group) From the viewpoint of film resistance, the thermosetting compound (D) preferably further contains a compound (D2) having an epoxy group.

[0144] The epoxy group is a group having a three-membered cyclic ether structure and includes an alicyclic epoxy group.

[0145] 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, glycerin triglycidyl ether, trimethylolpropane triglycidyl ether, polyethylene glycol diglycidyl ether, and polypropylene glycol diglycidyl ether; Polyglycidyl ether compounds of polyether polyols obtained by adding an alkylene oxide to a polyhydric alcohol such as ethylene glycol, propylene glycol, and glycerin; 3,4-Epoxycyclohexylmethyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-1-methylcyclohexyl-3,4-epoxy-1-methylhexanecarboxylate, 6-methyl-3,4-epoxycyclohexylmethyl-6-methyl-3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-3-methylcyclohexylmethyl-3,4-epoxy-3-methylcyclohexanecarboxylate, 3,4-epoxy-5-methylcyclohexylmethyl-3,4-epoxy-5-methylcyclohexanecarboxylate, 2-(3,4-epoxycyclohexyl-5,5-spiro-3,4-epoxy)cyclohexane-methanedioxane, bis(3,4-epoxycyclohexylmethyl) adipate, 3,4-epoxy-6-methylcyclohexanecarboxylate, methylenebis(3,4-epoxycyclohexane), ethylenebis(3,4-epoxycyclohexanecarboxylate), dioctyl epoxyhexahydrophthalate, 1-epoxyethyl-3,4-epoxycyclohexane, butanetetracarboxylic acid tetra(3,4-epoxycyclohexylmethyl) modified ε-caprolactone and other compounds having two or more 3,4-epoxycyclohexyl groups in the molecule; Examples include the 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2-bis(hydroxymethyl)-1-butanol and the like.

[0146] 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 Japan Epoxy Resins Co., Ltd.; Celoxide 2021, EHPE-3150, Epolide 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 manufactured by DIC Corporation, etc.

[0147] The compound (D2) having an epoxy group is preferably a compound having 2 to 50 epoxy groups in the molecule.

[0148] The epoxy equivalent of the compound (D2) having an epoxy group is preferably 50 to 400 g / eq, more preferably 100 to 200 g / eq. The epoxy equivalent is defined as the mass of an epoxy compound containing 1 equivalent of epoxy groups.

[0149] From the viewpoint of film resistance, the compound (D2) having an epoxy group preferably contains a compound represented by the following general formula (2).

[0150] General formula (2)

Chemical formula

[0151] In the general formula (2), R represents a group obtained by removing m hydroxyl groups from an m-valent alcohol, m represents an integer from 1 to 6, and n represents an integer from 1 to 30.

[0152] R represents a group obtained by removing m hydroxyl groups from an m-valent alcohol. 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 in which they are bonded. Examples of the alkyl group having 2 to 20 carbon atoms include ethyl group, methyl group, ethyl group, propyl group, isopropyl group, 2,2-dimethylpropyl group, butyl group, isobutyl group, tert-butyl group, 3,3-dimethylbutyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, etc. Among these, a branched alkyl group having 3 to 12 carbon atoms is more preferable. m represents an integer from 1 to 6, and n represents an integer from 1 to 30. When m is 2 or more, n in the groups within each pair of parentheses in the general formula (2) may be the same or different.

[0153] Examples of the compound represented by the general formula (2) include an adduct of 1,2-epoxy-4-(2-oxiranyl)cyclohexane with 2,2-bis(hydroxymethyl)-1-butanol. Commercially available products include EHPE-3150 and EHPE-3150CE manufactured by Daicel Corporation.

[0154] The acid value of the compound (D2) having an epoxy group is preferably 10 mgKOH / g or less.

[0155] The compound (D2) having an epoxy group can be used alone or in combination of two or more.

[0156] The content of the compound (D2) having an epoxy group is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, in 100% by mass of the non-volatile content of the curable composition.

[0157] 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.

[0158] [Silane coupling agent (E)] From the viewpoint of film resistance, the curable composition of the present invention preferably further contains a silane coupling agent (E).

[0159] The silane coupling agent (E) is a compound having a hydrolyzable group. The hydrolyzable group is a group directly bonded to a silicon atom and capable of forming a siloxane bond by 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, and the like. Among these, from the viewpoint of film resistance, an alkoxy group is preferable. Examples of the alkoxy group include a methoxy group, an ethoxy group, a butoxy group, and the like. From the viewpoints of film resistance, developability after storage, and line width stability after storage, an ethoxy group is preferable.

[0160] 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, and the like. Among these, from the viewpoint of film resistance, an epoxy group is preferable.

[0161] The silane coupling agent (E) is not particularly limited, and known compounds can be used. For example, 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. can be mentioned. Among these, from the viewpoints of film resistance, developability after storage, and line width stability after storage, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane are preferable.

[0162] Commercially available silane coupling agents (E) include, for example, KBM-302, KBM-402, KBM-403, KBE-402, KBE-403, KBM-4803, KBM-602, KBM-603, KBM-903, KBE-9103P, KBM-573, KBM-6803, KBM-1003, KBE-1003, 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-12-1048, X-12-50, X-12-5263HP, etc. manufactured by Shin-Etsu Chemical Co., Ltd.

[0163] The silane coupling agent (E) may also be of the polymer type. The polymer type includes the polysiloxane type and the organic polymer type.

[0164] The polysiloxane type is a compound in which the hydrolyzable group is bonded to a polymer having a polysiloxane skeleton in the main chain. 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.

[0165] The organic polymer type is a silane coupling agent (E) in which the hydrolyzable group is bonded to an organic polymer having an organic structure in the main chain. 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.

[0166] The silane coupling agent (E) can be used alone or in combination of two or more.

[0167] The content of the silane coupling agent (E) is preferably 0.1 to 10% by mass, more preferably 0.2 to 5% by mass, based on 100% by mass of the non-volatile content of the curable composition.

[0168] The curable composition of the present invention preferably contains one or more of a pigment (F) and a dye (G). Thereby, the transmittance of each wavelength region of the optical filter can be controlled.

[0169] [Pigment (F)] From the viewpoint of film resistance, the pigment (F) is more preferable for the curable composition of the present invention.

[0170] 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) may be either an inorganic pigment or an organic pigment, or an inorganic pigment and an organic pigment may be used in combination. The pigment (F) also includes organic-inorganic composites.

[0171] When the curable composition of the present invention is used for a color filter, the pigment (F) is preferably a colored pigment. The colored pigments 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 filter, the pigment (F) is preferably a near-infrared absorbing pigment. The near-infrared absorbing pigments can be used alone or in combination of two or more. When used for a near-infrared transmission filter, the pigment (F) is preferably an achromatic pigment (black) or a combination of two or more colored pigments used as black. Further, a near-infrared absorbing pigment may be used in combination.

[0172] (Colored pigment) 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 mentioned.

[0173] Examples of the colored pigments include red pigments such as C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, the pigments described in JP-A-2014-134712, the pigments described in Patent No. 6368844, and the like.

[0174] Examples of the orange pigments include C.I. Pigment Orange 36, 38, 43, 64, 71, 73, and the like.

[0175] 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 JP-A-2012-226110 are exemplified.

[0176] Further, examples of the yellow pigment include a metal azo pigment containing at least one anion selected from the group consisting of mono, di, tri, and tetra anions of an azo compound represented by the following general formula (3) and its azo compounds in 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).

[0177] General formula (3)

Chemical formula

[0178] In general formula (3), two R1s each independently represent -OH, -NH2, -NH-CN, an acylamino group, an alkylamino group, or an arylamino group, and two R2s each independently represent -OH or -NH2.

[0179] General formula (4)

Chemical formula

[0180] In the general formula (4), the three R3s each independently represent a hydrogen atom or an alkyl group.

[0181] Examples of the metal azo pigment include those described in, for example, JP-A-2014-12838, JP-A-2017-171912, JP-A-2017-171913, JP-A-2017-171914, JP-A-2017-171915, JP-A-2022-61494, and the like.

[0182] Examples of the green pigments include C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, 64, 65, 66, etc.

[0183] Examples of the blue pigments include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, 80, 87, 88, etc.

[0184] Examples of the violet pigments include C.I. Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc.

[0185] 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 pigment described later, it can be obtained (combined) using two or more colored pigments selected from the group consisting of red pigments, yellow pigments, green pigments, blue pigments, and violet pigments. Examples of the combinations include, for example, the following embodiments. (1) It contains a yellow pigment and a violet pigment. (2) It contains a red pigment, a yellow pigment, and a violet pigment. It contains a red pigment, a yellow pigment, and a blue pigment. It contains a red pigment, a yellow pigment, and a green pigment. It contains a yellow pigment, a blue pigment, and a purple pigment. It contains a red pigment, a yellow pigment, a blue pigment, and a purple pigment. It contains a yellow pigment, a blue pigment, a green pigment, and a purple pigment.

[0186] For the aspect of (1) above, for example, the yellow pigment is one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the purple pigment is C.I. Pigment Violet 23. For the aspect of (2) above, for example, the red pigment is one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment is one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the purple pigment is C.I. Pigment Violet 23. For the aspect of (3) above, for example, the red pigment is one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment is one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the blue pigment is one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6. For the aspect of (4) above, for example, the red pigment is one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment is one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, and the green pigment is one or more selected from C.I. Pigment Green 7, 36, 58, 59, 63. For the aspect of (5) above, for example, the yellow pigment is one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, the blue pigment is one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6, and the purple pigment is C.I. Pigment Violet 23. In the aspect of (6) above, for example, the red pigment is one or more selected from C.I. Pigment Red 177, 254, 291, 295, 296, the yellow pigment is one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, the blue pigment is one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6, and the purple pigment is C.I. Pigment Violet 23. In the aspect of (7) above, for example, the yellow pigment is one or more selected from C.I. Pigment Yellow 139, 185, 231, 233, the blue pigment is one or more selected from C.I. Pigment Blue 15:3, 15:4, 15:6, the green pigment is one or more selected from C.I. Pigment Green 7, 36, 58, 59, 63, and the purple pigment is C.I. Pigment Violet 23.

[0187] Table 1 shows the preferred mass ratios (mass %) of the chromatic pigments in each aspect.

[0188]

Table 1

[0189] These combinations of the chromatic pigments of (1) to (7) above are preferable when the curable composition of the present invention is used for a near-infrared transmission filter.

[0190] (achromatic pigment) The achromatic pigment is not particularly limited, and known achromatic pigments can be used. For example, 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, silica, 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 and the like described in JP-A No. 2011-075786, WO 2013 / 061621, JP-A No. 2015-047520, JP-A No. 2015-164881, JP-A No. 1-170601, JP-A No. 2-34664, JP-A No. 2007-302836, JP-T No. 2010-534726, JP-T No. 2012-515233 may be mentioned.

[0191] (Near-infrared absorbing pigment) The near-infrared absorbing pigment is a compound having a maximum absorption in the wavelength range of 700 to 2,000 nm, and may 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). Further, a near-infrared absorbing organic pigment and a near-infrared absorbing inorganic pigment may be used in combination. 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, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, croconium compounds, porphyrin compounds, etc. can be mentioned. Among these, from the viewpoints of near-infrared absorbability and heat resistance, naphthalocyanine compounds, pyrrolopyrrole compounds, squarylium compounds, and indigo compounds are preferable, and naphthalocyanine compounds, squarylium compounds, and indigo compounds are more preferable.

[0192] Cyanine compounds are described in, for example, International Publication No. 2006 / 006573, International Publication No. 2010 / 073857, Japanese Patent Application Laid-Open No. 2013-241598, Japanese Patent Application Laid-Open No. 2016-113501, Japanese Patent Application Laid-Open No. 2016-113504, etc.; phthalocyanine compounds are described in, for example, Japanese Patent Application Laid-Open No. 4-23868, Japanese Patent Application Laid-Open No. 06-192584, Japanese Patent Application Laid-Open No. 2000-63691, International Publication No. 2014 / 208514, Japanese Patent Application Laid-Open No. 2022-022070, Japanese Patent Application Laid-Open No. 2022-110262, etc.; naphthalocyanine compounds are described in, for example, Japanese Patent Application Laid-Open No. 11-152414, Japanese Patent Application Laid-Open No. 2000-86919, Japanese Patent Application Laid-Open No. 2009-29955, International Publication No. 2018 / 186490, Japanese Patent Application Laid-Open No. 2022-123689, Japanese Patent Application Laid-Open No. 2022-091099, Japanese Patent No. 7182049, etc.; indigo compounds are described in, for example, Japanese Patent Application Laid-Open No. 2013-230412, etc.; immonium compounds are described in, for example, Japanese Patent Application Laid-Open No. 2005-336150, Japanese Patent Application Laid-Open No. 2007-197492, Japanese Patent Application Laid-Open No. 2008-88426, Japanese Patent Application Laid-Open No. 2022-184710, Japanese Patent Application Laid-Open No. 2023-01394, etc.; anthraquinone compounds are described in, for example, Japanese Patent Application Laid-Open No. 62-903, Japanese Patent Application Laid-Open No. 1-172458, etc.; pyrrolopyrrole compounds are described in, for example, Japanese Patent Application Laid-Open No. 2009-263614, Japanese Patent Application Laid-Open No. 2010-90313, Japanese Patent Application Laid-Open No. 2011-068731, International Publication No. 2021 / 039205; squarylium compounds are described in, for example, Japanese Patent Application Laid-Open No. 2011-132361, Japanese Patent Application Laid-Open No. 2016-142891, International Publication No. 2017 / 135359, International Publication No. 2018 / 225837, Japanese Patent Application Laid-Open No. 2019-001987, International Publication No. 2020 / 054718, International Publication 2020 / 189459, etc.; croconium compounds are described in International Publication No. 2019 / 021767; porphyrin compounds are described in, for example, Japanese Patent Application Laid-Open No. 2006-209059, International Publication No. 2022 / 131191, etc.

[0193] The near-infrared absorbing inorganic pigment is not particularly limited, and known near-infrared absorbing inorganic pigments can be used. For example, metal oxide particles or metal particles such as indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, cesium tungsten oxide, lanthanum boride, copper, nickel, silver, and gold can be mentioned.

[0194] The pigment (F) can be used alone or in combination of two or more.

[0195] The content of the pigment (F) is preferably 0.5 to 60% by mass, more preferably 1 to 50% by mass, in 100% by mass of the non-volatile content of the curable composition.

[0196] The pigment (F) is preferably used after being refined. The refining method is not particularly limited, and for example, wet grinding, dry grinding, or the dissolution precipitation method can all be used. Among these, the salt milling treatment by the kneader method, which is a type of wet grinding, is preferable. The average primary particle diameter determined by TEM (transmission electron microscope) of the refined pigment is preferably 5 to 90 nm. From the viewpoint of dispersibility, the average primary particle diameter is more preferably 10 to 70 nm.

[0197] For the salt milling treatment, a resin may be added as necessary. 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 include natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. Among these, it is preferably solid at room temperature, water-insoluble, and partially soluble in organic solvents. 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).

[0198] [Dye (G)] The dye (G) is not particularly limited, and known dyes can be used. For example, acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, building dyes, sulfur dyes, etc. can be mentioned. Further, derivatives thereof and lake pigments obtained by lake-forming dyes are also mentioned.

[0199] The acid dye preferably has an acidic group such as a sulfonic acid or a carboxylic acid. Further, a salt-forming compound which is a salt of an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound is preferable. Further, a salt-forming compound which is a salt of a resin component having these functional groups and an acid dye is also preferable. Further, the salt-forming compound is easily obtained a curable composition excellent in resistance (light resistance, solvent resistance) by sulfonamidation and modification to a sulfonic acid amide compound. Further, a salt-forming compound of an acid dye and a compound having an onium base is also preferable because it is excellent in resistance (light resistance, solvent resistance). The compound having an onium base is preferably a resin having a cationic group.

[0200] The basic dye can be used as it is, but a salt-forming compound which forms a salt with an organic acid, perchloric acid or a metal salt thereof is preferable. The salt-forming compound of the basic dye is preferable because it is excellent in resistance (light resistance, solvent resistance) and affinity with a pigment. Further, as the anion component acting as a counter ion in the salt-forming compound of the basic dye, an organic sulfonic acid, an organic sulfuric acid, a fluorine group-containing phosphorus anion compound, a fluorine group-containing boron anion compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, and a salt-forming compound obtained by forming a salt with an acid dye are preferable. In addition, the resistance of the salt-forming compound is further improved when it contains a polymerizable unsaturated group in the molecule.

[0201] The chemical structure of the dye (G) is derived from a dye selected from, for example, azo dyes, disazo dyes, azomethine dyes (such as indoaniline dyes and indophenol dyes), dipyrromethene dyes, quinone dyes (such as benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, and anthrapyridone dyes), carbonium dyes (such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, and acridine dyes), quinoneimine dyes (such as oxazine dyes and thiazine dyes), azine dyes, polymethine dyes (such as oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, and croconium dyes), quinophthalone dyes, phthalocyanine dyes, naphthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and their metal complex dyes, etc.

[0202] Among these, from the viewpoint of color characteristics such as hue, color separation property, and color unevenness, a pigment structure derived from a pigment selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, naphthalocyanine dyes, and subphthalocyanine dyes is preferred, and a pigment structure derived from a pigment selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes is more preferred.

[0203] The dye (G) can be used alone or in combination of two or more.

[0204] The content of the dye (G) is preferably 0.5 to 60% by mass, more preferably 1 to 50% by mass, in 100% by mass of the non-volatile content of the curable composition.

[0205] [Pigment Derivative (H)] The curable composition of the present invention can contain a pigment derivative (H). When the pigment derivative (H) is used, the pigment (F) can be stably dispersed.

[0206] 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 mentioned. Specifically, compounds having an acidic substituent such as a sulfo group, a carboxy group, a phosphoric acid group, and amine salts thereof, compounds having a basic substituent such as a sulfonamide group and a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group and a phthalimidoalkyl group can be mentioned. 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, threne compounds, naphthalocyanine compounds, and the like.

[0207] Specifically, as the pyrrolopyrrole-based pigment derivatives, there are those described in JP-A No. 2001-220520, WO 2009 / 081930, WO 2011 / 052617, WO 2012 / 102399, JP-A No. 2017-156397, WO 2018 / 101189; as the phthalocyanine-based pigment derivatives, there are those described in JP-A No. 2007-226161, WO 2016 / 163351, JP-A No. 2017-165820, Patent No. 5753266; as the anthraquinone-based pigment derivatives, there are those described in JP-A No. 63-264674, JP-A No. 09-272812, JP-A No. 10-245501, JP-A No. 10-265697, JP-A No. 2007-079094, WO 2009 / 025325; as the quinacridone-based pigment derivatives, there are those described in JP-A No. 48-54128, JP-A No. 03-9961, JP-A No. 2000-273383; as the dioxazine-based pigment derivatives, there are those described in JP-A No. 2011-162662; as the thiazine indigo-based pigment derivatives, there are those described in JP-A No. 2007-314785; as the triazine-based pigment derivatives, there are those described in JP-A No. 61-246261, JP-A No. 11-199796, JP-A No. 2003-165922, JP-A No. 2003-168208, JP-A No. 2004-217842, JP-A No. 2007-314681; as the benzisoindole-based pigment derivatives, there are those described in JP-A No. 2009-57478; as the quinophthalone-based pigment derivatives, there are those described in JP-A No. 2003-167112, JP-A No. 2006-291194, JP-A No. 2008-31281, JP-A No. 2012-226110; as the naphthol-based pigment derivatives, there are those described in JP-A No. 2012-208329, JP-A No. 2014-5439; as the squarylium-based pigment derivatives, there is WO 2020 / 054718; as the azo-based pigment derivatives, there are JP-A No. 2001-172520, JP-A No. 2012-172092; as the acidic substituents, there is JP-A No. 2004-307854; as the basic substituents, there are JP-A No. 2002-201377, JP-A No. 2003-171594, JP-A No. 2005-181383, JP-A No. 2005-213404, etc. Known dye derivatives described therein can be mentioned.In these documents, they may be described as derivatives, dye derivatives, dispersants, dispersion aids, pigment dispersants or simply compounds, etc., but they are synonymous with the pigment derivative (H).

[0208] The pigment derivative (H) is preferably added during the micronization of the above-described pigment (F) or during the dispersion treatment of the pigment (F) described later. The average primary particle diameter of the pigment derivative (H) is preferably 5 to 200 nm.

[0209] The pigment derivative (H) can be used alone or in combination of two or more kinds.

[0210] The content of the pigment derivative (H) is preferably 1 to 50 parts by mass, more preferably 2 to 40 parts by mass, based on 100 parts by mass of the pigment (F).

[0211] [Dispersion resin (I)] The curable composition of the present invention can contain a dispersion resin (I). The dispersion resin (I) can stably disperse the pigment (F) which is a component of the curable composition.

[0212] As the dispersion resin (I), a resin having an adsorption group with high affinity for the pigment (F) is preferable. The adsorption group preferably has one or more of a basic group and an acidic group.

[0213] Examples of the basic group include groups containing a nitrogen atom such as a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic ring, etc.

[0214] Examples of the acidic group include a carboxyl group, a phosphoric acid group, and a sulfonic acid group, etc.

[0215] Examples of the resin species of the dispersion resin (I) include urethane resins, polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyamino amidine salts, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) and a polyester having a free carboxyl group and salts thereof, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, water-soluble resins and water-soluble polymer compounds such as polyvinyl alcohol and polyvinylpyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide addition compounds, phosphate ester-based, and the like.

[0216] Examples of the structure of the dispersion resin (I) include a chain random structure, a chain block structure, a graft structure, a comb structure, and a star structure. Among these, from the viewpoint of dispersion stability, a chain block structure, a graft structure, and a comb structure are preferred.

[0217] From the viewpoint of film resistance, 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, and a blocked isocyanate group.

[0218] 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.

[0219] 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., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc. manufactured by Lubrizol Japan, EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. manufactured by BASF Japan, Ajisuper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd., resins described in JP-A No. 2008-029901, JP-A No. 2009-155406, JP-A No. 2010-185934, JP-A No. 2011-157416, WO 2008 / 007776, JP-A No. 2008-029901, JP-A No. 2009-155406, JP-A No. 2010-185934, JP-A No. 2011-157416, JP-A No. 2009-251481, JP-A No. 2007-23195, JP-A No. 1996-143651, etc.

[0220] The dispersion resin (I) can be used alone or in combination of two or more.

[0221] From the viewpoint of dispersion stability, the content of the dispersion resin (I) is preferably 3 to 200 parts by mass, more preferably 5 to 150 parts by mass with respect to 100 parts by mass of the pigment (F).

[0222] [Sensitizer (J)] The curable composition of the present invention can contain a sensitizer (J).

[0223] The sensitizer (J) is not particularly limited, and known sensitizers can be used. For example, chalcone compounds, unsaturated ketones typified by dibenzalacetone, 1,2-diketone compounds typified by benzyl and camphorquinone, benzoin compounds, fluorene compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, polymethine dyes such as cyanine compounds, merocyanine compounds, oxonol compounds, acridine compounds, azine compounds, thiazine compounds, oxazine compounds, indoline compounds, azulene compounds, azulenium compounds, squarylium compounds, porphyrin compounds, tetraphenylporphyrin compounds, triarylmethane compounds, tetrabenzoporphyrin compounds, tetrapyrazinoporphyrazine compounds, phthalocyanine compounds, tetraazaporphyrazine compounds, tetraquinoxalyloporphyrazine compounds, naphthalocyanine compounds, subphthalocyanine compounds, pyrylium compounds, thiopyrylium compounds, tetraphyrin compounds, annulene compounds, spiropyran compounds, spirooxazine compounds, thiospiropyran compounds, metal arene complexes, organoruthenium complexes, or benzophenone compounds, etc. Among these, thioxanthone compounds and benzophenone compounds are preferred.

[0224] The sensitizer (J) can be used alone or in combination of two or more kinds.

[0225] The content of the sensitizer (J) is preferably 10 to 400 parts by mass, more preferably 20 to 300 parts by mass, per 100 parts by mass of the polymerization initiator (C).

[0226] [Curing agent (curing accelerator)] In order to assist the curing of the thermally crosslinkable compound (D), a curing agent (curing accelerator) can be used in combination in the curable composition of the present invention. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. Examples of the curing agent include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (for example, triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (for example, dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (for example, triphenylphosphine, etc.), S-triazine derivatives (for example, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.).

[0227] The curing agent can be used alone or in combination of two or more kinds.

[0228] The content of the curing agent is preferably 0.01 to 15 parts by mass per 100 parts by mass of the thermally crosslinkable compound (D).

[0229] [Thiol-based chain transfer agent (K)] The curable composition of the present invention can contain a thiol-based chain transfer agent (K).

[0230] The thiol-based chain transfer agent (K) is not particularly limited, and known thiol-based chain transfer agents can be used. For example, monofunctional thiol compounds such as thiophenol, 2-mercaptobenzothiazole, 2-mercaptobenzimidazole, 2-mercaptobenzoxazole, 2-mercapto-5-methoxybenzothiazole, 2-mercapto-5-benzimidazole, butanethiol, octanethiol, 1-dodecanethiol, methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, octyl 3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate; monofunctional thiol compounds having a hydroxyl group or an acidic group such as 2-mercaptoethanol, 1-thioglycerol, thioglycolic acid, 2-mercaptobenzoic acid, 3-mercaptobenzoic acid, 4-mercaptonicotinic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 4-mercaptobutanoic acid, octyl thioglycolate, mercaptosuccinic acid, 11-mercaptoundecanoic acid, 2-mercaptoethanesulfonic acid; polythiol compounds such as hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakis(3-mercaptopropionate), tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. can be mentioned.

[0231] The thiol-based chain transfer agent (K) can be used alone or in combination of two or more kinds.

[0232] The content of the thiol-based chain transfer agent (K) is preferably 0.1 to 10% by mass in 100% by mass of the nonvolatile content of the curable composition.

[0233] [Polymerization inhibitor (L)] From the viewpoints of developability after storage and line width stability after storage, the curable composition of the present invention preferably contains a polymerization inhibitor (L).

[0234] The polymerization inhibitor (L) is not particularly limited, and known polymerization inhibitors can be used. For example, phenol compounds, hydroquinone compounds, benzoquinone compounds, phenothiazine compounds, catechol compounds, nitrobenzene compounds, nitroso compounds, amine compounds, hindered amine compounds, phosphorus compounds and the like can be mentioned. Among these, from the viewpoints of developability after storage and line width stability after storage, it is preferable to contain a hydroquinone compound.

[0235] Examples of the phenol compound 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], pentaerythrityl-tetrakis[3-(3,5-di-t-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 and the like.

[0236] Hydroquinone compounds include, for example, hydroquinone, methylhydroquinone, ethylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone, 2,6-di-tert-butylhydroquinone, 2,3,5-trimethylhydroquinone, 2,5-dichlorohydroquinone, and the like.

[0237] Benzoquinone compounds include, for example, p-benzoquinone, methyl-p-benzoquinone, 2-tert-butyl-1,4-benzoquinone, 2,5-diphenyl-p-benzoquinone, chloro-p-benzoquinone, 2,5-dichloro-p-benzoquinone, 2,6-dichloro-p-benzoquinone, tetrachloro-p-benzoquinone, tetrabromo-p-benzoquinone, and the like.

[0238] Phenothiazine compounds include, for example, phenothiazine, 3,7-dioctylphenothiazine, 3,7-dicumylphenothiazine, 10-methylphenothiazine, 2-methoxyphenothiazine, and the like.

[0239] Catechol compounds include, for example, 4-methylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, and the like.

[0240] Nitrobenzene compounds include, for example, nitrobenzene, o-dinitrobenzene, m-dinitrobenzene, p-dinitrobenzene, 2,4-dinitrotoluene, dinitrodurene, 2,2-diphenyl-1-picrylhydrazyl, and the like.

[0241] Nitroso compounds include, for example, nitrosobenzene, 2-nitrosotoluene, 1,2,4,5-tetramethyl-3-nitrosobenzene, 4-nitrosophenol, 1-nitroso-2-naphthol, 2-nitroso-1-naphthol, 4-nitrosodiphenylamine, and the like.

[0242] Examples of amine compounds include N,N-diphenylamine, 4,4'-dicumyl-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-benzenediamine, N-(1,4-dimethylpentyl)-N'-phenyl-1,4-benzenediamine, N-(1,3-dimethylbutyl)-N'-phenyl-1,4-benzenediamine, and the like.

[0243] 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, and the like.

[0244] Phosphorus compounds include, for example, triphenylphosphine, triphenyl phosphite, triethyl phosphite, tris(isodecyl) phosphite, tris(tridecyl) phosphite, phenyl diisooctyl phosphite, phenyl diisodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl isodecyl phosphite, diphenyl tridecyl phosphite, phosphonic acid [1,1-diphenyl-4,4'-diylbis(tetrakis-2,4-bis(1,1-dimethylethyl)phenyl)] ester, triphenyl phosphite, tris(nonylphenyl) phosphite, 4,4'-isopropylidenediphenol alkyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(biphenyl) phosphite, distearyl pentaerythritol diphosphite, di(2,4-di-tert-butylphenyl) pentaerythritol diphosphate, di(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, and the like.

[0245] The polymerization inhibitor (L) can be used alone or in combination of two or more.

[0246] The content of the polymerization inhibitor (L) is preferably 0.01 to 0.5% by mass in 100% by mass of the nonvolatile content of the curable composition.

[0247] [Antioxidant (M)] The curable composition of the present invention can contain an antioxidant (M).

[0248] The antioxidant (M) is not particularly limited, and known antioxidants can be used. For example, hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, and hydroxylamine compounds can be mentioned. Among these, hindered phenol compounds, hindered amine compounds, phosphorus compounds, and sulfur compounds are preferred.

[0249] Hindered phenolic compounds include, for example, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-tert-butylphenyl)-butane, 4,4'-butylidene-bis-(2-tert-butyl-5-methylphenol), stearyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] Undecane, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-tert-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-tert-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-tert-butyl-4-hydroxy-hydrocinnamide), iso-octyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-tert-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-tert-butylphenyl)propionic acid] ethylenebisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, 2,2'-thio-bis-(6-tert-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-tert-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, etc. may be mentioned.

[0250] Commercially available products include, for example, Adeka Stab 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 Ltd.; and Cyanox CY-1790, CY-2777 manufactured by Sankyo Chemical Co., Ltd., etc.

[0251] Hindered amine compounds include, for example, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, the polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], the ester of 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis〔4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazine-2-yl〕-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) decanedioate, the reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyrpiperidyl)[[3,5-bis(1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate methyl 1,2,2,6,6-pentamethyl-4-pyrpiperidyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,Examples thereof include 6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc.

[0252] Commercially available products include, 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 Ltd.; and Cyasorb-UV-3346, UV-3529, UV-3853 manufactured by Sankyo Chemical Co., Ltd., etc.

[0253] Phosphorus compounds include, for example, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl) 2-ethylhexyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidenediphenyldiphosphite, diphenylmono(2-ethylhexyl) phosphite, diphenylisodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4-biphenyldiphosphonite, tris(tridecyl) phosphite, phenylisooctyl phosphite, phenylisodecyl phosphite, phenyldi(tridecyl) phosphite, diphenylisooctyl phosphite, diphenyltridecyl phosphite, 4,4'-isopropylidenediphenol alkyl phosphite, trisononylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(nonylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-tert-butylphenol) diphosphite, hexatridecyl 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl)butane triphosphite, 3,5-di-tert-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-tert-butylphenyl) phosphite, sodium-2,2-methylene-bis(4,6-di-tert-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4-di-tert-butyl-6-methylphenyl) phosphite, etc.

[0254] Commercially available products include, for example, Adeka Stab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA Corporation, IRGAFOS 168 manufactured by BASF Japan Ltd., Hostanox P-EPQ manufactured by Clariant Chemicals, etc.

[0255] Examples of sulfur-based compounds include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diyl bis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2'-thio-diethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, etc.

[0256] Commercially available products include, for example, Adeka Stab AO-412S, AO-503 manufactured by ADEKA Corporation, KEMINOX PLS manufactured by Chemipro Kasei Co., Ltd., etc.

[0257] The antioxidant (M) can be used alone or in combination of two or more.

[0258] The content of the antioxidant (M) is preferably 0.5 to 5.0% by mass in 100% by mass of the non-volatile components of the curable composition.

[0259] [Leveling agent (N)] The curable composition of the present invention can contain a leveling agent (N).

[0260] 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 diol-based leveling agents, etc. can be mentioned.

[0261] Commercially available silicone leveling agents include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 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.; TegoGlide432, 440, 450, TegoWet250, 260, 265, 270, 280 manufactured by Evonik; MEGAFACE EFS-131, EFS-321, EFS-521, EFS-801 manufactured by DIC, etc.

[0262] Commercially available fluorine-based leveling agents include, for example, Surflon S-242, 243, 420, 611, 651, 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 554, 555, 556, 558, 559, 560, 561, 570, 575, 576, R-01, R-40, R-40-LM, R-41, 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 Co., Ltd.; 602A of the phthalgent manufactured by Neos Co., etc.

[0263] Commercially available acrylic leveling agents include, for example, BYK-350, 352, 354, 355, 358, 380, 381, 392, 394 manufactured by BYK Chemie; Polyflow 57, 77, 95 manufactured by Kyoeisha Chemical Co., Ltd., etc.

[0264] Commercially available acetylene diol-based leveling agents include, for example, Surfynol 420, 440, 465, 485, SE, DF110D, DE85 manufactured by Nissin Chemical Industry Co., Ltd.; Orfin E1004, 1010, etc.

[0265] The leveling agent (N) can be used alone or in combination of two or more.

[0266] 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, in 100% by mass of the non-volatile content of the curable composition.

[0267] [Storage stabilizer (O)] The curable composition of the present invention can contain a storage stabilizer (O).

[0268] The storage stabilizer (O) is not particularly limited, and known compounds can be used. For example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as tert-butylpyrocatechol, tetraethylphosphine, and tetraphenyl, and phosphites, etc. can be mentioned.

[0269] The content of the storage stabilizer (O) is preferably 0.05 to 5% by mass in 100% by mass of the non-volatile content of the curable composition.

[0270] [UV absorber (P)] The curable composition of the present invention can contain a UV absorber (P).

[0271] The UV absorber (P) is not particularly limited, and known UV absorbers can be used. For example, benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds, etc. can be mentioned.

[0272] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, a mixture of 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and straight-chain alkyl ester, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-tert-butyl-4-methylphenol, 2-(3,5-di-tert-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0273] Commercially available products include, for example, TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, 1130 manufactured by BASF Japan Ltd., Adeka Stab LA-29, LA-31RG, LA-32, LA-36 manufactured by ADEKA Corporation, KEMISORB 71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

[0274] Triazine compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, and the like.

[0275] Commercially available products include, for example, KEMISORB 102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN 400, 405, 460, 477, 479, 1577ED manufactured by BASF Japan Ltd., Adeka Stab LA-46, LA-F70 manufactured by ADEKA Corporation, CYASORB UV-1164 manufactured by Sankyo Chemical Co., Ltd., and the like.

[0276] Benzophenone compounds include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3 water temperature, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like.

[0277] Commercially available products include, for example, KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., SEESORB 101, 107 manufactured by Cypro Kasei Co., Ltd., Adeka Stab 1413 manufactured by ADEKA Corporation, UV-12 manufactured by Sankyo Chemical Co., Ltd., and the like. Salicylic acid ester compounds include, for example, phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like.

[0278] The content of the ultraviolet absorber (P) is preferably 0.1 to 5.0% by mass in 100% by mass of the non-volatile components of the curable composition.

[0279] [Organic solvent (Q)] The curable composition of the present invention can contain an organic solvent (Q).

[0280] The organic solvent (Q) is not particularly limited, and known compounds can be used. For example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-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 monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone,Dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, etc. may be mentioned.

[0281] From the environmental perspective, it is preferable that the curable composition of the present invention substantially does not contain organic solvents which are aromatic hydrocarbons (such as toluene, xylene, benzene, chlorobenzene, etc.). Substantially not containing means that in the curable composition, it is 50 mass ppm or less, preferably 30 mass ppm or less, and more preferably 10 mass ppm or less.

[0282] The organic solvent (Q) can be used alone or in combination of two or more.

[0283] The content of the organic solvent (Q) is preferably an amount such that the non-volatile content of the curable composition is 5 to 60% by mass.

[0284] [Other components] The curable composition of the present invention can contain components other than those described above (hereinafter, also simply referred to as other components). Examples of other components include surfactants, acid generators, salt generators, curing catalysts, light extinguishing agents, semiconductor nanocrystals, semiconductor materials, organic electroluminescence 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.

[0285] [Content of specific metal elements] In the curable composition of the present invention, it is preferable that 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 500 mass ppm or less.

[0286] A curable composition having a total amount of specific metal elements within the above range is excellent in dispersion stability and sensitivity even after storage over time. The content of specific metal elements can be measured by inductively coupled plasma optical emission spectrometry (ICP).

[0287] [Water content] In the curable composition of the present invention, it is preferable that the water content contained in the curable composition is 2.0 mass% or less.

[0288] A curable composition having a water content within the above range is excellent in dispersion stability and sensitivity even after storage over time. The water content can be measured by a known method such as the Karl Fischer method.

[0289] [Method for producing curable composition] The curable composition of the present invention can be prepared by mixing the above-described components. When adjusting, the components may be compounded all at once, or may be sequentially compounded 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), it is preferable to perform a dispersion treatment. 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 blending and mixing an alkali-soluble resin (A), a polymerizable compound (B), a polymerization initiator (C), a thermally crosslinkable compound (D), etc. into the dispersion. Note that the timing of blending each material is arbitrary. Also, the dispersion step can be performed multiple times.

[0290] Examples of the disperser for performing the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor.

[0291] The average dispersed particle diameter (secondary particle diameter) of the particles in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. When having an appropriate particle diameter, a curable composition with high dispersion stability is easily obtained.

[0292] As a method for measuring the average dispersed particle diameter (secondary particle diameter), for example, using Microtrac UPA-EX150 of Nikkiso Co., Ltd. that employs the dynamic light scattering method (FFT power-spectrum method), the particle permeability is set to the absorption mode, the particle shape is set to non-spherical, and the D50 particle diameter is set as the average diameter. As the dilution solvent for measurement, the organic solvent used for dispersion is used respectively, and when measuring the sample immediately after sample adjustment for the sample treated with ultrasonic waves, a result with less variation is easily obtained and is preferable.

[0293] It is preferable to remove coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and mixed dust from the curable composition by means such as centrifugation, filtration with a sintered filter or a membrane filter. The curable composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0294] The curable composition of the present invention is preferably used for pattern formation by a photolithography method. Note that the present invention is not limited thereto.

[0295] <Film> The film of the present invention is a film formed from the above-described curable composition. The film is preferably a patterned film, but can also be used as a flat film without forming a pattern.

[0296] [Method for manufacturing film] The method for manufacturing the film is not particularly limited, and known methods can be used. For example, it can be manufactured through steps such as applying the curable composition of the present invention onto a substrate and drying.

[0297] [Coating step] Examples of the substrate include substrates made of materials such as glass, resin, and silicone. The glass may be colorless and transparent, and depending on the application, colored glass such as blue glass may be used. 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 to 10 mm. An organic light-emitting layer may be formed on these substrates. Also, an imaging element such as a CCD or CMOS may be formed on the substrate. Further, a primer layer may be provided on the substrate as necessary for improving adhesion to the upper layer, preventing diffusion of substances, and planarizing the surface.

[0298] The coating method is not particularly limited, and known methods can be used. For example, the dropping method, slit coating method, spray method, roll coating method, spin coating method, casting coating method, inkjet method, flexographic printing, screen printing, gravure printing, offset printing, etc. can be mentioned.

[0299] The thickness of the film can be appropriately adjusted according to the purpose. The thickness of the film is preferably 0.05 to 20.0 μm, and more preferably 0.3 to 10.0 μm.

[0300] [Drying step] Drying of the film coated on the substrate is not particularly limited, and known methods can be used. For example, a reduced-pressure drying method using a vacuum drying apparatus, a heating drying method using a hot plate, an IR oven, a convection oven, etc., and a method combining these can be mentioned.

[0301] The drying temperature and time can be adjusted as appropriate. The drying temperature is preferably about 50 to 130 °C, and the drying time is preferably about 5 seconds to 5 minutes.

[0302] Next, a pattern is formed. Examples of the method for forming a pattern include a photolithography method and a dry etching method. Among these, the photolithography method is preferred. Note that when used as a flat film, the step of forming a pattern may not be performed.

[0303] 〔Exposure step〕 In the exposure step, the layer formed by coating and drying is exposed to a specific pattern through a mask using an exposure apparatus such as a stepper. Thereby, the exposed portion can be cured. Examples of the active energy ray used for exposure include ultraviolet rays such as g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm). Also, light with a wavelength of 300 nm or less can be used. Examples of light with a wavelength of 300 nm or less include KrF line (wavelength 248 nm), ArF line (wavelength 193 nm), etc. When using light of a specific wavelength for irradiation, an optical filter can also be used. Also, during exposure, the light may be continuously irradiated for exposure, or the light irradiation and pause may be repeated in a short time (for example, at the millisecond level or less) cycle for exposure (pulse exposure). Also, a combination of multiple active energy rays or exposure in multiple steps can be performed.

[0304] 〔Development step〕 Next, by performing an alkali development treatment, the layer of the unexposed portion is eluted in the alkali developer, and only the cured portion remains to obtain a patterned film. Alkaline developers include, for example, aqueous solutions containing alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene. These alkaline compounds can be used in combination of two or more. In addition to the alkaline compound and water, the alkaline developer may contain a surfactant or an organic solvent. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, roughness and peeling of the pattern are suppressed, and the residual film rate after development is improved. Examples of the development method include dip method, spray method, paddle method, etc. The development temperature is preferably 15 to 40 °C. After alkaline development, it is preferably washed with pure water.

[0305] 〔Post-baking step〕 After development, heat treatment (post-baking) is performed. The film resistance is improved by post-baking. The temperature is preferably 70 to 300 °C, more preferably 80 to 240 °C. The time is preferably about 2 minutes to 2 hours. When a material with low heat resistance is used for the substrate, when a substrate having an organic electroluminescence element as a light-emitting layer is used, or from the viewpoint of reducing environmental load, 180 °C or lower is preferable, 150 °C or lower is more preferable, and 130 °C or lower is particularly preferable.

[0306] The curable composition of the present invention is preferably used at a post-baking temperature of 180 °C or lower, more preferably 150 °C or lower, and particularly preferably 130 °C or lower.

[0307] <Optical filter> The optical filter of the present invention has the above-mentioned film. The optical filter is used, for example, in color filters, black matrices, light-shielding filters, antireflection filters, infrared cut filters, infrared transmission filters, microlenses, etc. The optical filter of the present invention can be manufactured, for example, by the same method as the above-mentioned film.

[0308] <Solid-state imaging device> The solid-state imaging device of the present invention has the above-mentioned optical filter. The solid-state imaging device includes the optical filter of the present invention and is not particularly limited as long as it functions as a solid-state imaging device. For example, the following configurations can be mentioned.

[0309] On a substrate, it has a plurality of photodiodes that constitute the light-receiving area of a solid-state imaging device (such as a CCD image sensor, a CMOS image sensor, etc.) and transfer electrodes made of polysilicon, etc. On the photodiodes and the transfer electrodes, it has a light-shielding film with an opening only in the light-receiving part of the photodiodes. On the light-shielding film, it has a device protection film made of silicon nitride, etc., formed so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiodes. On the device protection film, it has the optical filter (color filter) of the present invention. Further, it may have a configuration having condensing means (for example, microlenses, etc. The same applies hereinafter) on the device protection film and below the optical filter (on the side closer to the substrate), or a configuration having condensing means on the optical filter. Also, the filter may have a structure in which a cured film forming each colored pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls. In this case, the partition walls are preferably of a low refractive index with respect to each colored pixel. The imaging device provided with the solid-state imaging device of the present invention can be used in various applications such as digital cameras, electronic devices having an imaging function (such as mobile phones, smartphones, etc.), in-vehicle cameras, surveillance cameras, etc.

[0310] <Image display device> The image display device of the present invention has the above-mentioned optical filter. Examples of the image display device include liquid crystal displays, organic EL displays, etc. The form used in the image display device only needs to function as an image display device and is not particularly limited. For example, the following configuration of a liquid crystal display can be mentioned.

[0311] The liquid crystal display includes a color filter, a counter substrate having a 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 TN method, the IPS method, the OCB method, and the MVA method. The counter substrate can be appropriately selected and used according to the driving method. For the liquid crystal layer, various liquid crystals with different dielectric anisotropies and mixtures thereof can be used according to the driving method.

[0312] Specifically, it is described in "Next-generation Liquid Crystal Display Technology" (written by Tatsuo Uchida, published by Kogyo Chosa Kai, Inc. in 1994), "Electronic Display Devices" (written by Akio Sasaki, published by Kogyo Chosa Kai, Inc. in 1990), "Display Devices" (written by Junsho Ibuki, published by Sangyo Tosho Co., Ltd. in 1989), etc.

[0313] <Infrared Sensor> The infrared sensor of the present invention has the above optical filter. The form used in the infrared sensor is not particularly limited as long as it includes the optical filter of the present invention and functions as an infrared sensor. For example, the following configurations can be mentioned.

[0314] On the substrate, there are a plurality of photodiodes constituting the light-receiving area of a solid-state imaging device (such as a CCD image sensor, a CMOS image sensor, etc.) and transfer electrodes made of polysilicon. On these photodiodes and transfer electrodes, there is a light-shielding film with an opening only in the light-receiving part of the photodiode. On this light-shielding film, there is a device protection film, and further on this device protection film, there is the optical filter of the present invention. Furthermore, a configuration having a condensing means (such as a microlens, etc. The same applies hereinafter) on the device protection film and below the optical filter (closer to the substrate side), or a configuration having a condensing means on the optical filter may also be used.

[0315] FIG. 1 is a schematic cross-sectional view showing a configuration example of an infrared sensor including the optical filter of the present invention. The infrared sensor 100 shown in FIG. 1 includes a solid-state imaging device 110.

[0316] The imaging region provided on the solid-state imaging device 110 is configured by combining an infrared cut filter 111 and a color filter 112.

[0317] The infrared cut filter 111 transmits light in the visible light region (for example, light having a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light having a wavelength of 800 to 1,300 nm).

[0318] The color filter 112 is a color filter in which pixels that transmit and absorb light of a specific wavelength 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.

[0319] A resin film 114 that can transmit light having a wavelength transmitted through the infrared transmission filter 113 is disposed between the infrared transmission filter 113 and the solid-state imaging device 110.

[0320] The infrared transmission filter 113 is a filter that has visible light shielding properties and transmits infrared light of a specific wavelength. The infrared transmission filter 113 preferably blocks light having a wavelength of 400 to 830 nm and transmits light having a wavelength of 900 to 1,300 nm.

[0321] 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.

[0322] In the form shown in FIG. 1, the resin film 114 is disposed, but the infrared transmission filter 113 may be formed instead of the resin film 114.

[0323] According to this infrared sensor, since image information can be captured simultaneously, motion sensing or the like for recognizing a target to be detected for motion is possible. Further, according to this infrared sensor, since distance information can be obtained, photographing an image including 3D information or the like is also possible. Furthermore, this infrared sensor can also be used as a biometric sensor.

Example

[0324] Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the examples. Note that "parts" means "parts by mass" and "%" means "% by mass". In the present invention, the non-volatile content or the non-volatile concentration refers to the mass residue after standing in an oven at 110 ° C for 3 hours.

[0325] Prior to the examples, each measurement method will be described.

[0326] 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 follows.

[0327] (Molecular weight) The number average molecular weight (Mn) and weight average molecular weight (Mw) were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the apparatus. Two separation columns were connected in series, and "TSK-GEL SUPER HZM-N" was connected in a pair for both packing materials and used. The oven temperature was 40 ° C, a tetrahydrofuran (THF) solution was used as the eluent, and the measurement was performed at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent composed of 1 mass% of the above eluent and 20 microliters were injected. The molecular weight is a polystyrene conversion value.

[0328] (Acid value of resin) To 0.5 - 1 g of the resin solution, 80 ml of acetone and 10 ml of water were added, and the mixture was stirred until uniformly dissolved. Using a 0.1 mol / L aqueous KOH solution as the titrant, titration was performed using an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd., "COM-555"), and the acid value (mgKOH / g) was measured. Then, from the acid value of the resin solution and the non-volatile content concentration of the resin solution, the acid value per non-volatile content of the resin was calculated.

[0329] (Amine value of the resin) The amine value of the resin is the value obtained by converting the total measured amine value (mgKOH / g) to non-volatile content in accordance with the method of ASTM D 2074.

[0330] (Absorption coefficient) 0.001 g of the 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 (manufactured by Hitachi High-Technologies Corporation, "U-3010"), the absorbance of each concentration of the measurement solution at a wavelength of 365 nm was measured, and the absorption coefficient (L / mol·cm) was calculated from the slope when the horizontal axis was the molar concentration and the vertical axis was the absorbance.

[0331] (Production of alkali-soluble resin (A)) (Solution of alkali-soluble resin (A1-1) having a hydroxyl group-containing monomer unit (a1)) 100.0 parts of propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMAc) was placed in a reaction vessel equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe, and a stirring device. While injecting nitrogen gas into the reaction vessel, it was heated to 120 °C, and at the same temperature, 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 were added dropwise from the dropping pipe over 2.5 hours as a mixture, and a polymerization initiator, 5.0 parts of azobisisobutyronitrile dissolved in PGMAc, was added dropwise over 2.5 hours to carry out a polymerization reaction. After the dropping was completed, it was stirred at 120 °C for another 2 hours to obtain a precursor. Next, the inside of the reaction vessel was purged with air, 0.30 part of tris(dimethylaminomethyl)phenol 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. Thereby, the epoxy group of glycidyl methacrylate was reacted with the carboxyl group of acrylic acid, and while generating a hydroxyl group by cleavage of the epoxy group of glycidyl methacrylate, a polymerizable unsaturated group was introduced. Next, 48.68 parts (0.32 mol) of tetrahydrophthalic anhydride and 0.5 part of triethylamine were added as a modifying compound, and the reaction was carried out at 120 °C for 4 hours. Thereby, a part of the hydroxyl group generated by cleavage of the epoxy group of glycidyl methacrylate was reacted with tetrahydrophthalic anhydride to introduce a carboxyl group. Then, PGMAc was added so that the non-volatile content became 40% by mass to prepare a solution of an alkali-soluble resin (A1-1) having a hydroxyl group-containing monomer unit (a1). The weight average molecular weight (Mw) was 10,000 and the acid value was 77 mgKOH / g.

[0332] (Solution of alkali-soluble resin (A1-2) to (A1-6) having hydroxyl group-containing monomer unit (a1)) Except for changing the formulation of the alkali-soluble resin (A1-1) as described in Table 2, the alkali-soluble resins (A1-2) to (A1-6) having a hydroxyl group-containing monomer unit (a1) were synthesized in the same manner as the alkali-soluble resin (A1-1). In addition, PGMAc was added to each to make the non-volatile content 40% by mass. The weight-average molecular weight of the resin was adjusted by appropriately changing the amount of the polymerization initiator used. The formulation amounts in Table 2 are in mol%.

[0333] [Table 2]

[0334] Aronix M-110 described in Table 2 is para-cumylphenol ethylene oxide-modified acrylate manufactured by Toagosei Co., Ltd., and Karenz MOI-DEM is malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester) manufactured by Resonance Co., Ltd.

[0335] (Other alkali-soluble resin (A2-1) solution) 160 parts of PGMAc was placed in a reaction vessel equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirring device. While injecting nitrogen gas into the reaction vessel, it was heated to 120 °C, and at the same 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, and 1.0 part of azobisisobutyronitrile as a polymerization initiator were dropped from the dropping tube over 2.5 hours and reacted. After the dropping was completed, stirring was continued at 120 °C for another 2 hours to continue the reaction. Then, 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.

[0336] [Polymerizable compound (B)] (Polyfunctional urethane (meth)acrylate (B1-1) having a secondary amine or tertiary amine structure) Into 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 added. Then, while stirring, the temperature was raised to 50 °C. Next, 160.8 parts of N-methylethanolamine were gradually dropped into the flask from the dropping funnel while the reaction was carried out. After the dropping was completed, stirring was carried out at 50 °C for 2 hours to continue the reaction. Next, the temperature was raised to 100 °C, and 198.3 parts of isophorone diisocyanate were gradually dropped into the flask from the dropping funnel while the reaction was carried out. After the dropping was completed, the reaction was carried out with stirring at 100 °C for 4 hours to obtain an alicyclic polyfunctional urethane acrylate having a tertiary amine structure.

[0337] (Polyfunctional urethane (meth)acrylate (B1-2) having a secondary or tertiary amine structure) Into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and an air inlet tube, 998.4 parts of ditrimethylolpropane tetraacrylate, 2.0 parts of 4-methoxyphenol, 2.0 parts of triphenyl phosphite, and 2.0 parts of phenothiazine were added. Then, while stirring, the temperature was raised to 50 °C. Next, 160.8 parts of N-methylethanolamine were gradually dropped into the flask from the dropping funnel while the reaction was carried out. After the dropping was completed, stirring was carried out at 50 °C for 2 hours to continue the reaction. Next, the temperature was raised to 100 °C, and 198.3 parts of isophorone diisocyanate were gradually dropped into the flask from the dropping funnel while the reaction was carried out. After the dropping was completed, the reaction was carried out with stirring at 100 °C for 4 hours to obtain an alicyclic polyfunctional urethane acrylate having a tertiary amine structure.

[0338] (Polyfunctional urethane (meth)acrylate (B1-3) having a secondary or tertiary amine structure) Into 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. Then, while stirring, the temperature was raised to 50°C. Next, 160.8 parts of N-methylethanolamine were gradually dropped into the flask from the dropping funnel while carrying out the reaction. After the dropping was completed, the mixture was stirred at 50°C for 2 hours to continue the reaction. Next, the temperature was raised to 100°C, and 198.3 parts of isophorone diisocyanate were gradually dropped into the flask from the dropping funnel while carrying out the reaction. After the dropping was completed, the reaction was carried out while stirring at 100°C for 4 hours to obtain an alicyclic polyfunctional urethane acrylate having a tertiary amine structure.

[0339] (Polyfunctional urethane (meth)acrylate (B1-4) having a secondary or tertiary amine structure) Into 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. Then, while stirring, the temperature was raised to 50°C. Next, 160.8 parts of N-methylethanolamine were gradually dropped into the flask from the dropping funnel while carrying out the reaction. After the dropping was completed, the mixture was stirred at 50°C for 2 hours to continue the reaction. Next, the temperature was raised to 100°C, and 149.7 parts of hexamethylene diisocyanate were gradually dropped into the flask from the dropping funnel while carrying out the reaction. 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.

[0340] (Polyfunctional urethane (meth)acrylate (B1-5) having a secondary or tertiary amine structure) Into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and an air introduction 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 added. Then, while stirring, the temperature was raised to 50 °C. Next, while gradually dropping 160.8 parts of N-methylethanolamine from the dropping funnel into the flask, the reaction was carried out. After the dropping was completed, the mixture was stirred at 50 °C for 2 hours to continue the reaction. Next, the temperature was raised to 100 °C, and while gradually dropping 155.0 parts of 2,4-tolylene diisocyanate from the dropping funnel into the flask, 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.

[0341] <Production of thermally crosslinkable compound (D)> (Solution of thermally crosslinkable compound (D1-1)) A flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube was purged with nitrogen, charged with 200 parts of hexamethylene diisocyanate and 6.6 parts of trimethylolpropane, heated to 80 °C while stirring, and reacted while stirring for 2 hours. Then, it was cooled to 60 °C, tetrabutylammonium acetate was added, and phosphoric acid was added to stop the reaction when the yield reached 45%. After filtering the reaction solution, unreacted hexamethylene diisocyanate was removed using a thin-film evaporation device to obtain a trimethylolpropane adduct of hexamethylene diisocyanate. Next, a flask equipped with a stirrer, a thermometer, a reflux condenser, and a nitrogen introduction tube was purged with nitrogen, charged with 100 parts of an adduct of hexamethylene diisocyanate and trimethylolpropane and 39 parts of n-butyl acetate, and while stirring, a mixed solution of 78 parts of diethyl malonate and 0.7 part of 28% sodium methylate solution was gradually added. After the addition was completed, the temperature was raised to 60 °C and the reaction was carried out while stirring for 6 hours. Then, butanol was added so that the nonvolatile content became 60% by mass to obtain a compound which is an adduct of hexamethylene diisocyanate blocked with an active methylene compound having a weight average molecular weight of 1,200.

[0342] (Thermosetting Compound (D1-2) Solution) A flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube was purged with nitrogen, charged with 1,000 parts of hexamethylene diisocyanate, heated to 60 °C with stirring, and 0.1 part of trimethylbenzylammonium hydroxide was added. After 4 hours, when the conversion rate reached 38%, 0.2 g of phosphoric acid was added to stop the reaction. After filtering the reaction solution, unreacted hexamethylene diisocyanate was removed using a thin-film evaporator to obtain an isocyanurate form of hexamethylene diisocyanate. Next, a flask equipped with a stirrer, thermometer, reflux condenser, and nitrogen inlet tube was purged with nitrogen, charged with 100 parts of the isocyanurate form of hexamethylene diisocyanate and 39 parts of n-butyl acetate, and a mixed solution of 92 parts of diethyl malonate and 0.8 part of 28% sodium methylate solution was gradually added with stirring. After the addition was complete, the temperature was raised to 60 °C and the reaction was carried out with stirring for 6 hours. Then, butanol was added so that the non-volatile content became 60% by mass to obtain a compound that is an isocyanurate form of hexamethylene diisocyanate blocked with an active methylene compound having a weight average molecular weight of 985.

[0343] <Production of Pigment (F)>[ (Near-Infrared Absorbing Pigment (F-11)) 40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 part of p-toluenesulfonic acid monohydrate were mixed in 400 parts of toluene, heated and stirred in an atmosphere of nitrogen gas, 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 was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. 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 the mixture was heated and stirred in an atmosphere of nitrogen gas and refluxed for 8 hours. The water generated during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the solvent was distilled off, and while stirring the resulting reaction mixture, 200 parts of hexane was added. After filtering off the resulting black-brown precipitate, it was washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain a 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), and kneaded at 60 °C for 12 hours. Next, the kneaded mixture was put into warm water, stirred for 1 hour while heating to about 80 °C to make it into a slurry state, and filtration and washing with ion-exchanged water were repeated a plurality of times, and then dried at 80 °C for a whole day and night and pulverized to obtain a micronized near-infrared absorbing pigment (F-11).

[0344] Chemical formula (5) [Chemical formula]

[0345] (Near-infrared absorbing pigment (F-12)) In a reaction vessel, 26 parts of phthalonitrile, 143 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene), and 34 parts of aluminum trichloride were mixed and stirred, and after heating up, refluxed at 136 °C for 5 hours. The reaction solution cooled to 30 °C while stirring was poured into a mixed solvent consisting of 5,000 parts of methanol and 10,000 parts of ion-exchanged water while stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2,000 parts of methanol and 4,000 parts of ion-exchanged water, and dried to obtain Compound a. Next, in a reaction vessel, 140 parts of Compound a was added to 1,500 parts of concentrated sulfuric acid under an ice bath, and stirred for 1 hour. Subsequently, this sulfuric acid solution was poured into 1,000 parts of cold water at 3 °C, and the generated 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 dried to obtain Compound b. 5 parts of diphenylphosphoric acid was added to 200 parts of N-methylpyrrolidone, and after thorough stirring and mixing, it was heated to 50 °C. To this solution, 10 parts of Compound b was added little by little, and then stirred at 90 °C for 120 minutes. The end point of the reaction was confirmed by, for example, dropping the reaction solution onto filter paper and taking the point where there was no bleeding as the end point. Subsequently, this reaction solution was poured into 2,000 parts of ion-exchanged water, and the resulting precipitate was filtered and washed repeatedly with ion-exchanged water several times, and then dried to obtain a mixture of compounds represented by the following chemical formula (6) (mass ratio: n1:n2:n3:n4 = 7:19:59:15), a near-infrared absorbing pigment (F-12). Subsequently, it was micronized in the same manner as the near-infrared absorbing pigment (F-11).

[0346] Chemical formula (6)

Chem.

[0347] (Near-infrared absorbing pigment (F-13)) According to the description in International Publication No. 2019 / 058882, a 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).

[0348] Chemical formula (7)

Chem.

[0349] (Near-infrared absorbing pigment (F-14)) In a reaction vessel, 10.7 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. Then, 95.2 parts of a 1 mol / l toluene solution of titanium tetrachloride was added dropwise. After the dropwise addition, 10.0 parts of indigo was added and refluxed for 10 hours. After completion of the reaction, methanol was added and filtered to obtain a green powder. This was separated with dichloromethane and water, and the organic layer was concentrated to obtain 14.6 parts of Compound c. In a reaction vessel, 13.5 parts of compound c, 9.0 parts of bis(2,4-pentanedionato)zinc(II), and 120 parts of tetrahydrofuran were mixed and stirred. After raising the temperature, the mixture was stirred at 40 °C for 5 hours. The reaction solution, which was cooled to 30 °C while stirring, was poured into 500 parts of methanol with stirring to obtain a blue slurry. This slurry was filtered, washed with 500 parts of methanol, washed multiple times with 500 parts of ion-exchanged water, and dried to obtain a near-infrared absorbing pigment (F-14), which is a mixture of compounds represented by the following chemical formula (8) (mass ratio of dimer:trimer:tetramer = 81:17:2). Subsequently, it was micronized in the same manner as the near-infrared absorbing pigment (F-11).

[0350] Chemical formula (8) [Chemical formula]

[0351] <Production of dispersion resin (I)> (Dispersion resin (I-1) solution) Into a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic dianhydride, 650 parts of PGMAc, and 0.2 part of monobutyltin oxide as a catalyst were charged. After purging with nitrogen gas, the mixture was reacted at 120 °C for 5 hours (first step). It was confirmed by measuring the acid value that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of 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, and 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added and reacted for 12 hours (second step). It was confirmed by measuring the non-volatile content that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate, and 0.1 part of hydroquinone were charged. Based on the isocyanate group at 2,270 cm -1The reaction was carried out until the disappearance of the peak (third step). After cooling, PGMAc was added so that the non-volatile content became 30% by mass to obtain a comb-shaped dispersion resin (I-1) solution having a polymerizable unsaturated group. The acid value was 68 mgKOH / g and the weight average molecular weight was 13,000.

[0352] (Dispersion resin (I-2) solution) Into a reaction vessel equipped with a gas introduction tube, thermometer, condenser, and stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of iso-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50°C, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and a solution prepared by adding 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of PGMAc was added while reacting for 7 hours. It was confirmed by non-volatile content measurement that 95% had reacted. 19 parts of pyromellitic dianhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 100°C for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. After cooling, PGMAc was added so that the non-volatile content became 30% by mass to obtain a comb-shaped dispersion resin (I-2) solution. The acid value was 70 mgKOH / g and the weight average molecular weight was 8,500.

[0353] (Dispersion resin (I-3) solution) Into a reactor equipped with a gas inlet pipe, a condenser, a stirring blade, 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, the mixture was stirred at 50 °C for 1 hour, and the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 100 parts of PGMAc were charged. Under a nitrogen stream, the temperature was raised to 110 °C to initiate the polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile content. Next, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as the second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were added to this reactor, and the mixture was stirred while maintaining at 110 °C in a nitrogen atmosphere to continue the reaction. Two hours after the addition, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of non-volatile content. After cooling, PGMAc was added so that the non-volatile content became 30% by mass to prepare a dispersion resin (I-3) solution having a chain block structure. The amine value was 169.8 mgKOH / g.

[0354] (Dispersion resin (I-4) solution) According to Example A3 of International Publication No. 2022 / 172607, a dispersion 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.

[0355] <Production of dispersion>[[]] (Dispersion 1) After stirring and mixing the following raw materials uniformly, they were dispersed for 3 hours using zirconia beads with a diameter of 0.5 mm in an Igar mill (Mini Model M-250 MKII manufactured by Igar Japan Co., Ltd.), and then filtered through a filter with a pore size of 1.0 μm to prepare Dispersion 1. The non-volatile content was 22.5% by mass. Pigment (F-1): 15.00 parts ​Dispersed resin (I-1) solution: 10.00 parts Dispersed resin (I-3) solution: 15.00 parts Organic solvent (Q-1): 60.00 parts

[0356] (Dispersions 2 to 14) Dispersions 2 to 14 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts described in Table 3-1 and Table 3-2 were changed.

[0357]

Table 3-1

[0358]

Table 3-2

[0359] Each of the components described in Table 3-1 and Table 3-2 is as follows.

[0360] [Pigment (F)] F-1: C.I. Pigment Green 63 F-2: C.I. Pigment Green 58 F-3: C.I. Pigment Blue 15:3 F-4: C.I. Pigment Blue 15:6 F-5: C.I. Pigment Yellow 139 F-6: C.I. Pigment Yellow 150 F-7: C.I. Pigment Yellow 231 F-8: C.I. Pigment Red 177 F-9: C.I. Pigment Red 254 F-10: C.I. Pigment Violet 23

[0361] Pigments (F-1) to (F-10) were each refined by salt milling treatment, washed sufficiently with ion-exchanged water so that the curable composition would have the above-described specific metal amount, and then dried before use.

[0362] [Pigment Derivative (H)] [Chem.]

[0363] [Organic Solvent (Q)] Q-1: Propylene Glycol Monomethyl Ether Acetate

[0364] [Production of Curable Composition] [Example 1] (Curable Composition 1) The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain Curable Composition 1. The non-volatile content was 15.00% by mass. Dispersion 1: 12.10 parts Dispersion 3: 4.10 parts Dispersion 5: 6.70 parts Dispersion 7: 4.10 parts Solution of Alkali-Soluble Resin (A1-1) Having Hydroxyl Group-Containing Monomer Unit (a1): 2.00 parts Polyfunctional Urethane (Meth)acrylate (B1-1) Having Secondary Amine or Tertiary Amine Structure: 0.50 part Other (Meth)acrylate (B2-1): 0.10 part Other (Meth)acrylate (B2-4): 1.00 part Other (Meth)acrylate (B2-5): 1.00 part Other (Meth)acrylate (B2-7): 0.40 part Photopolymerization Initiator (C1-1): 0.15 part Photopolymerization Initiator (C1-2): 0.15 part Thermal Polymerization Initiator (C2-1): 0.45 part Compound (D1-3) Having Block Isocyanate Group: 5.00 parts Compound (D2-1) Having Epoxy Group: 0.30 part Silane Coupling Agent (E-1): 0.75 part Polymerization Inhibitor (L-1): 0.75 part Leveling Agent (N): 0.02 part Ultraviolet absorber (P): 0.15 part Organic solvent (Q): 60.28 parts

[0365] [Examples 2 to 59 and Comparative Example 1] (Curable compositions 2 to 60) Curable compositions 2 to 60 were prepared in the same manner as in Example 1, except that the raw materials and amounts described in Tables 4-1 to 4-6 were changed from those of curable composition 1 of Example 1.

[0366]

Table 4-1

[0367]

Table 4-2

[0368]

Table 4-3

[0369]

Table 4-4

[0370]

Table 4-5

[0371]

Table 4-6

[0372] Regarding each of the raw materials described in Tables 4-1 to 4-6, it is as follows.

[0373] [Polymerizable compound (B)] (Polyfunctional urethane (meth) acrylate having a secondary amine or tertiary amine structure) B1-6: CN9906NS (manufactured by Arkema, aliphatic polyfunctional urethane acrylate having a tertiary amine structure)

[0374] (Others (meth)acrylate (B2)) B2-1: 1,6 - hexanediol diacrylate (in the general formula (1), a compound where R1 and R2 are hydrogen atoms, l and m are 0, and n is 6) B2-2: 1,9 - nonanediol diacrylate (in the general formula (1), a compound where R1 and R2 are hydrogen atoms, l and m are 0, and n is 9) B2-3: Tricyclodecane dimethanol diacrylate B2-4: Aronix M-306 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate, with pentaerythritol triacrylate being 65 - 70%) B2-5: Aronix M-510 (manufactured by Toagosei Co., Ltd., a trifunctional acrylate containing an acidic group) B2-6: Aronix M-350 (manufactured by Toagosei Co., Ltd., trimethylolpropane EO - modified triacrylate) B2-7: Aronix M-402 (manufactured by Toagosei Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate, with dipentaerythritol pentaacrylate being 30 - 40%)

[0375] [Polymerization initiator (C)] (Photoinitiator (C1)) C1-1: Adeka Arcles NCI-831E (manufactured by ADEKA, an oxime - based compound with an extinction coefficient of 13,410 L / mol·cm for light with a wavelength of 365 nm) C1-2: Irgacure OXE04 (manufactured by BASF Japan, an oxime - based compound with an extinction coefficient of 7,051 L / mol·cm for light with a wavelength of 365 nm) C1-3: Irgacure OXE02 (manufactured by BASF Japan, an oxime - based compound with an extinction coefficient of 2,401 L / mol·cm for light with a wavelength of 365 nm)

[0376] (Thermal initiator (C2)) C2-1: 1,1-bis(tert-hexylperoxy)cyclohexane (10-hour half-life temperature is 87.1 °C) C2-2: 2,2-bis(4,4-di-tert-butylperoxycyclohexyl)propane (10-hour half-life temperature is 94.7 °C) C2-3: di-tert-hexyl peroxide (10-hour half-life temperature is 116.4 °C) C2-4: dilauroyl peroxide (10-hour half-life temperature is 61.6 °C) C2-5: hydroperoxy(diisopropyl)benzene (10-hour half-life temperature is 145 °C)

[0377] [Thermosetting compound (D)] (Compound (D1) having a blocked isocyanate group) D1-3: Duranate MF-K60B (manufactured by Asahi Kasei Corporation, isocyanurate form of hexamethylene diisocyanate blocked with an active methylene compound, non-volatile content 60% by mass) D1-4: BI7982 (manufactured by Baxenden Chemical, isocyanurate form of hexamethylene diisocyanate blocked with a pyrazole compound, non-volatile content 70% by mass) D1-5: BI7984 (manufactured by Baxenden Chemical, isocyanurate form of hexamethylene diisocyanate blocked with an oxime compound, non-volatile content 75% by mass) D1-6: BI7951 (manufactured by Baxenden Chemical, isocyanurate form of isophorone diisocyanate blocked with a pyrazole compound, non-volatile content 75% by mass) D1-7: Takenate B-830 (manufactured by Mitsui Chemicals, adduct form of toluene diisocyanate blocked with an oxime compound, non-volatile content 55.5% by mass)

[0378] (Compound (D2) having an epoxy group) D2-1: EHPE-3150 (manufactured by Daicel Corporation, compound represented by general formula (2), average number of epoxy groups is 15, epoxy equivalent is 170 - 190 g / eq) D2-2: Denacol EX-611 (manufactured by Nagase ChemteX Corporation, average number of epoxy groups is 4, epoxy equivalent is 155 - 175 g / eq)

[0379] [Silane coupling agent (E)] E-1: KBE-403 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltriethoxysilane) E-2: KBE-402 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropylmethyldiethoxysilane) E-3: KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-glycidoxypropyltrimethoxysilane) E-4: KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd., 3-methacryloxypropyltriethoxysilane)

[0380] [Polymerization inhibitor (L)] L-1: 1% solution of methylhydroquinone in propylene glycol monomethyl ether acetate L-2: 1% solution of p-methoxyphenol in propylene glycol monomethyl ether acetate

[0381] [Leveling agent (N)] N-1: BYK-330 (manufactured by BYK-Chemie GmbH, polyether-modified dimethylsiloxane) N-2: Block copolymer having the following structure (n:m = 50:50 (mol%)) The above N-1 and N-2 were mixed at a mass ratio of 8:2 to obtain the leveling agent (N).

[0382]

Chemical formula

[0383] [UV absorber (P)] P-1: Tinuvin 460 (manufactured by BASF Japan Ltd., hydroxyphenyltriazine-based compound) P-2: Tinuvin 326 (manufactured by BASF Japan Ltd., benzotriazole-based compound) The above P-1 and P-2 were mixed at a mass ratio of 5:5 to obtain the UV absorber (P).

[0384] [Organic solvent (Q)] Q-1: PGMAc Q-2: Propylene glycol monomethyl ether Q-3: 3-Methoxy-1-butanol Q-4: Ethyl 3-ethoxypropionate The above Q-1, Q-2, Q-3, and Q-4 were mixed at a mass ratio of 80:10:5:5 to obtain the organic solvent (Q).

[0385] [Evaluation of the curable composition] The following evaluations were performed on the obtained curable compositions 1 to 60. The evaluation results are shown in Table 5.

[0386] [Adhesion evaluation] The obtained curable composition was applied to a glass substrate (Eagle 2000 manufactured by Corning) with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm using a spin coater so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 90 °C for 2 minutes. Next, after cooling this 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, the illuminance was 30 mW / cm 2 , 100 mJ / cm 2 and exposed. Then, this substrate was spray-developed using an aqueous developer containing 0.12% of a nonionic surfactant and 0.04% of potassium hydroxide at 23 °C, washed with ion-exchanged water, air-dried, and post-baked in a clean oven at 110 °C for 30 minutes. The spray development was performed at the shortest time capable of forming a pattern without remaining development for the film of each curable composition, and this was defined as the appropriate development time. The patterns with widths of 5 to 25 μm on the evaluation substrate were observed with an optical microscope, and the remaining patterns were confirmed. The evaluation criteria are as follows, and 3 or more is considered practical. 5: Patterns of 10 μm or less remain. 4: Patterns of 15 μm or more remain. Patterns of 10 μm or less do not remain. 3: Patterns with dimensions of 20 μm or more remain. Patterns with dimensions of 15 μm or less do not remain. 2: Patterns with dimensions of 25 μm remain. Patterns with dimensions of 20 μm or less do not remain. 1: No patterns remain.

[0387] [Film Resistance Evaluation] The obtained curable composition was applied to a glass substrate (Eagle 2000 manufactured by Corning Inc.) measuring 100 mm in length × 100 mm in width and 0.7 mm in thickness using a spin coater so that the film thickness after drying was 2.0 μm, and then dried on a hot plate at 90 °C for 2 minutes. Next, after cooling this substrate to room temperature, using an ultra-high pressure mercury lamp, through a photomask with a 100-μm-wide stripe pattern, the illuminance was 30 mW / cm 2 , and it was exposed at 100 mJ / cm 2 . Thereafter, this 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, then washed with ion-exchanged water, air-dried, and post-baked in a clean oven at 110 °C for 30 minutes. The spray development was carried out at the shortest time capable of forming a pattern without any remaining development for the film formed from each curable composition. 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 observed using an optical microscope for the 100-μm-wide stripe pattern portion. The evaluation criteria are as follows, and a value of 3 or more is considered practical. 5: No change in appearance or color. 4: Slight wrinkles or the like occur, but there is no change in color. 3: Wrinkles or the like occur in part, but there is no change in color. 2: Wrinkles or the like occur over the entire surface, and it fades slightly. 1: Peeling or fading occurs.

[0388] [Developability Evaluation] The obtained curable composition was applied onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) measuring 100 mm in length × 100 mm in width and 0.7 mm in thickness using a spin coater so that the dry film thickness became 2.0 μm, and dried on a hot plate at 90°C for 2 minutes. Next, after cooling this substrate to room temperature, using an ultra-high pressure mercury lamp, the illuminance was 30 mW / cm 2 through a photomask with a 100-μm-wide stripe pattern, and exposed at 100 mJ / cm 2 . Thereafter, this 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 with ion-exchanged water and air-dried. The spray development was performed at the shortest time capable of forming a pattern without any remaining development for the film formed from each curable composition, and this was taken as the initial development time. The curable composition was put into a sealed container and stored at 40°C for 1 week, and developed under the same conditions as the initial evaluation. The evaluation criteria were as follows, and those with 3 or more were considered practical. 5: The development time after storage is in the range of 90% or more and 110% or less of the initial development time 4: The development time after storage is in the range of 80% or more and less than 90% of the initial development time, or more than 110% and 120% or less 3: The development time after storage is in the range of 70% or more and less than 80% of the initial development time, or more than 120% and 130% or less 2: The development time after storage is in the range of 60% or more and less than 70% of the initial development time, or more than 130% and 140% or less 1: The development time after storage is less than 60% of the initial development time or more than 140%

[0389] [Line Width Stability Evaluation] The obtained curable composition was applied onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) measuring 100 mm in length × 100 mm in width and 0.7 mm in thickness by spin coating so that the film thickness after drying became 2.0 μm, and dried on a hot plate at 90°C for 2 minutes. Next, after cooling this substrate to room temperature, using an ultra-high pressure mercury lamp, the illuminance was 30 mW / cm 2 and the exposure dose was 100 mJ / cm 2It was exposed. Then, this 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 with ion-exchanged water and air-dried. 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 a Nikon ECLIPSE LV100POL Model optical microscope, and this was defined as the initial line width (CD1). The curable composition was placed in a sealed container and stored at 40°C for one week. A pattern was fabricated and the line width was measured under the same conditions as the initial evaluation, and this was defined as the line width after storage (CD2). The evaluation criteria are as follows, and a value of 3 or more is considered practical. Formula (1): ΔCD = |CD2 - CD1| 5: ΔCD is less than 2 μm 4: ΔCD is 2 μm or more and less than 3 μm 3: ΔCD is 3 μm or more and less than 5 μm 2: ΔCD is 5 μm or more and less than 6 μm 1: ΔCD is 6 μm or more

[0390]

Table 5

Explanation of Symbols

[0391] 100 Infrared sensor 110 Solid-state imaging device 111 Infrared cut filter 112 Color filter 113 Infrared transmission filter 114 Resin film 115 Microlens 116 Planarization film

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) contains a polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure in which the (meth)acryloyl group is polyfunctional (however, excluding polyfunctional urethane (meth)acrylates having a cyclic amine), the polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure in which the (meth)acryloyl group is polyfunctional includes one or more selected from the group consisting of an alicyclic polyfunctional urethane (meth)acrylate having a secondary amine or tertiary amine structure, an aliphatic polyfunctional urethane (meth)acrylate having a secondary amine or tertiary amine structure, and an aromatic polyfunctional urethane (meth)acrylate having a secondary amine or tertiary amine structure, the polyfunctional urethane (meth)acrylate (B1) having a secondary amine or tertiary amine structure in which the (meth)acryloyl group is polyfunctional is a urethane reaction product of a Michael addition reaction product of a (meth)acrylate compound (X) and an amine compound (Y) having a hydroxyl group with a polyisocyanate compound (Z), the (meth)acrylate compound (X) is at least one selected from the group consisting of ethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerin tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolpropane EO or PO modified tri(meth)acrylate, ditrimethylolpropane EO or PO modified tetra(meth)acrylate, pentaerythritol EO or PO modified tetra(meth)acrylate, and dipentaerythritol EO or PO modified hexa(meth)acrylate, The amine compound (Y) having the hydroxyl group is at least one selected from the group consisting of ethanolamine, butanolamine, diethylene glycolamine, N-methylethanolamine, N-ethylethanolamine, N-propylethanolamine, N-isopropylethanolamine, N-butylethanolamine, N-isobutylethanolamine, N-methylbutanolamine, N-ethylbutanolamine, and N-butyl-4-hydroxybutylamine, The curable composition, wherein the thermally crosslinkable compound (D) contains a compound (D1) having a blocked isocyanate group using a blocking agent selected from the group consisting of an active methylene compound, a pyrazole compound, and an oxime compound.

2. The curable composition according to claim 1, wherein the polymerizable compound (B) further contains a (meth)acrylate (B2) other than the polyfunctional urethane (meth)acrylate (B1) having a secondary or tertiary amine structure in which the (meth)acryloyl group is polyfunctional.

3. The curable composition according to claim 1, wherein the blocked isocyanate group of the compound (D1) having a blocked isocyanate group has a structure protected by an active methylene compound.

4. The curable composition according to claim 1, wherein the alkali-soluble resin (A) contains an alkali-soluble resin (A1) having a hydroxyl group-containing monomer unit (a1).

5. The curable composition according to claim 1, further comprising a silane coupling agent (E).

6. A film formed from the curable composition according to any one of claims 1 to 5.

7. An optical filter having the film according to claim 6.

8. A solid-state imaging device having the optical filter according to claim 7.

9. An image display device having the optical filter according to claim 7.

10. An infrared sensor having the optical filter according to claim 7.

Images