Curable composition, method for producing pixel, film, solid-state imaging element, image display device, compound, and photosensitizer

Abstract

Disclosed are: a curable composition which contains a photopolymerization initiator, a polymerizable compound, and a compound represented by formula (1); and a method for producing a pixel, a film, a solid-state imaging element, and an image display device, each of which uses the above-described curable composition. In formula (1), R1 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group; R2 represents an alkyl group, an aryl group or a heteroaryl group; R3 to R7 each independently represent a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; and adjacent groups among R4 to R7 may be bonded to each other to form a ring.

Description

Curable composition, pixel manufacturing method, film, solid-state imaging device, image display device, compound, and photosensitizer

[0001] The present invention relates to a curable composition containing a photopolymerization initiator and a polymerizable compound. The present invention also relates to a pixel manufacturing method, a film, a solid-state imaging device, and an image display device using the curable composition. The present invention also relates to a compound and a photosensitizer.

[0002] Curable compositions containing a photopolymerization initiator and a polymerizable compound can be polymerized and cured by irradiation with light, and are therefore used in optical filters, photocurable inks, photosensitive printing plates, various photoresists, and the like.

[0003] Patent Document 1 discloses that pixels are formed by forming a pattern by a photolithography method using a curable composition containing a photopolymerization initiator, a polymerizable compound, and a compound represented by formula (I): １ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, or a hydroxy group; R ２ represents a halogen atom, an alkylcarbonyl group, an arylcarbonyl group, or a heteroarylcarbonyl group; R ３ and R ４ each independently represents a hydrogen atom, an alkyl group, an alkoxy group, or an alkylthio group; R ３ and R １ , R ４ and R １ may be bonded to each other to form a ring, R ５ represents an alkyl group, and n represents an integer of 0 to 3.

[0004] JP 2011-209655 A

[0005] Conventionally, when forming a pattern by photolithography using a curable composition, exposure is performed by irradiating the curable composition with i-line light (wavelength 365 nm) in a pattern. In Patent Document 1, exposure is also performed by irradiating the curable composition with i-line light.

[0006] In recent years, it has been considered to expose the substrate by irradiating it in a pattern with light having a wavelength of 150 to 300 nm, such as KrF radiation (wavelength 248 nm).

[0007] However, compared to i-line, conventional curable compositions tend to have insufficient sensitivity when exposed to light having a wavelength of 150 to 300 nm, such as KrF line. Furthermore, although the curable composition disclosed in Patent Document 1 can be cured with high sensitivity to exposure to light in the short wavelength region around 365 nm, the inventors' studies have revealed that even the curable composition disclosed in Patent Document 1 still has room for improvement in sensitivity when exposed to light having a wavelength of 150 to 300 nm, such as KrF line.

[0008] Therefore, an object of the present invention is to provide a curable composition having excellent sensitivity to light with a wavelength of 150 to 300 nm. Another object of the present invention is to provide a method for producing a pixel, a film, a solid-state imaging device, an image display device, a compound, and a photosensitizer.

[0009] The present invention provides the following:

[0010] <1> A curable composition containing a photopolymerization initiator, a polymerizable compound, and a compound represented by formula (1); In formula (1), R １ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group; R ２ represents an alkyl group, an aryl group, or a heteroaryl group; R ３ ~R ７ each independently represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; R ４ ~R ７ <2> The curable composition according to <1>, wherein the compound represented by formula (1) is a compound represented by formula (2); In formula (2), R ２１ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group; L ２１ represents a single bond or an alkylene group; R ２２ａ and R ２２ｂ each independently represents an alkyl group, R２２ａ and R ２２ｂ may be bonded to form a ring, R ２３ ~R ２７ each independently represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; R ２４ ~R ２７ <3> The curable composition according to <1>, wherein the compound represented by formula (1) is a compound represented by formula (3); In formula (3), R ３１ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group; L ３１ represents a single bond or an alkylene group having 1 to 4 carbon atoms; L ３２ Ha-(CR Ｌ１ R Ｌ２ ) ｐ represents -, and R Ｌ１ and R Ｌ２ each independently represents a hydrogen atom or an alkyl group, p represents an integer of 1 to 5, ３２ａ and R ３２ｂ each independently represents a hydrogen atom or an alkyl group; R ３３ ~R ３７ each independently represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; R ３４ ~R ３７ <4> The curable composition according to <1>, wherein the compound represented by formula (1) is a compound represented by formula (4); In formula (4), R ４１ represents a hydrogen atom, a halogen atom, a nitro group or an acyl group; R ４２ represents an alkyl group, an aryl group, or a halogen atom; R ４３ ~R ４７ each independently represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; R ４４ ~R ４７Among these, adjacent groups may be bonded to form a ring, and m represents an integer of 0 to 4. <5> The curable composition according to any one of <1> to <4>, containing 0.01 to 500 parts by mass of relative to 100 parts by mass of the photopolymerization initiator. <6> The curable composition according to any one of <1> to <5>, wherein the photopolymerization initiator contains an oxime compound having an indole skeleton. <7> The curable composition according to any one of <1> to <6>, further containing a colorant. <8> The curable composition according to any one of <1> to <7>, further containing an amine compound. <9> The curable composition according to any one of <1> to <8>, further containing a chain transfer agent. <10> A method for manufacturing a pixel, comprising the steps of: forming a curable composition layer on a support using the curable composition according to any one of <1> to <9>; patternwise exposing the curable composition layer by irradiating it with light having a wavelength of 150 to 300 nm; and developing and removing the unexposed areas of the curable composition layer. <11> A film obtained by curing the curable composition according to any one of <1> to <9>. <12> A solid-state imaging device comprising the film according to <11>. <13> An image display device comprising the film according to <11>. <14> A compound represented by formula (2a); In formula (2a), R ２１ａ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group; L ２１ａ represents an alkylene group having 1 to 4 carbon atoms; R ２２Ｌａ and R ２２Ｌｂ each independently represents an alkyl group, R ２２Ｌａ and R ２２Ｌｂ may be bonded to form a ring, R ２３ａ ~R ２７ａ each independently represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; R ２４ａ ~R ２７ａ Adjacent groups among these may be bonded to each other to form a ring. <15> A photosensitizer comprising the compound according to <14>.

[0011] According to the present invention, it is possible to provide a curable composition having excellent sensitivity to light with a wavelength of 150 to 300 nm. The present invention also provides a method for producing a pixel, a film, a solid-state imaging device, an image display device, a compound, and a photosensitizer.

[0012] The present invention will be described in detail below. In this specification, the term "to" is used to mean that the numerical values ​​before and after the term are included as the lower and upper limits. In the description of groups (atomic groups) in this specification, a term without specifying whether it is substituted or unsubstituted encompasses both unsubstituted groups (atomic groups) and substituted groups (atomic groups). For example, the term "alkyl group" encompasses not only unsubstituted alkyl groups (unsubstituted alkyl groups) but also substituted alkyl groups (substituted alkyl groups). In this specification, unless otherwise specified, "exposure" includes not only exposure using light but also drawing using particle beams such as electron beams and ion beams. Examples of light used for exposure include the bright line spectrum of a mercury lamp, far ultraviolet light typified by excimer lasers, extreme ultraviolet light (EUV light), X-rays, electron beams, and other actinic rays or radiation. As used herein, "(meth)acrylate" refers to either or both of acrylate and methacrylate, "(meth)acrylic" refers to either or both of acrylic and methacrylic, and "(meth)acryloyl" refers to either or both of acryloyl and methacryloyl. In the structural formulae herein, Me refers to a methyl group, Et refers to an ethyl group, Bu refers to a butyl group, and Ph refers to a phenyl group. As used herein, the weight-average molecular weight and number-average molecular weight are polystyrene-equivalent values ​​measured by GPC (gel permeation chromatography). As used herein, the term "total solids" refers to the total mass of all components of a composition excluding the solvent. As used herein, the term "pigment" refers to a coloring material that is difficult to dissolve in a solvent. As used herein, the term "process" refers not only to an independent process, but also to a process that cannot be clearly distinguished from other processes, as long as the intended effect of the process is achieved.

[0013] <Curable Composition> The curable composition of the present invention is characterized by containing a photopolymerization initiator, a polymerizable compound, and a compound represented by formula (1).

[0014] The curable composition of the present invention has high sensitivity to light with wavelengths of 150 to 300 nm. The detailed reasons for this effect are presumed to be as follows: The compound represented by formula (1) has effective absorption in the ultraviolet wavelength region around 150 to 300 nm and has the property of easily undergoing intersystem crossing to a triplet state. It is presumed that this allows the carbonyl group of the compound represented by formula (1) to form a biradical structure and have a hydrogen abstraction-type radical initiation function. It is also presumed that, when used in combination with a photopolymerization initiator, the compound also functions as a sensitizer, efficiently transferring triplet energy from the triplet state of the compound represented by formula (1) to the photopolymerization initiator used in combination. For these reasons, the curable composition of the present invention has high sensitivity to light with wavelengths of 150 to 300 nm, and when exposed to light with wavelengths of 150 to 300 nm, it can sufficiently promote the polymerization reaction of the polymerizable compound. Furthermore, sufficient polymerization can also proceed at the bottom of the film (the support side), allowing the formation of pixels with excellent adhesion.

[0015] Furthermore, the compound represented by formula (1) can appropriately absorb light having a wavelength of about 150 to 300 nm and suppress reflection of the exposure light from the support, thereby suppressing unevenness in the exposure amount in the film thickness direction due to interference, and thus suppressing surface roughness on the sidewalls of the pixels when the pixels are formed.

[0016] Furthermore, the compound represented by formula (1) has excellent absorbency for light having a wavelength of around 365 nm, and the curable composition of the present invention also has high sensitivity to light having a wavelength of around 365 nm.

[0017] The curable composition of the present invention preferably further contains a colorant. The curable composition containing a colorant is preferably used as a curable composition for an optical filter. Examples of the optical filter include a color filter, an infrared transmission filter, and an infrared cut filter, and a color filter is preferred.

[0018] The color filter may have colored pixels that transmit light of a specific wavelength. Examples of the colored pixels include red, green, blue, magenta, cyan, and yellow pixels. The colored pixels of the color filter may be formed using a curable composition containing a chromatic colorant.

[0019] The infrared cut filter preferably has a maximum absorption wavelength in the wavelength range of 700 to 1800 nm, more preferably in the wavelength range of 700 to 1300 nm, and even more preferably in the wavelength range of 700 to 1000 nm. The transmittance of the infrared cut filter over the entire wavelength range of 400 to 650 nm is preferably 70% or more, more preferably 80% or more, and even more preferably 90% or more. The transmittance at at least one point in the wavelength range of 700 to 1800 nm is preferably 20% or less. The ratio of the absorbance Amax at the infrared cut filter's maximum absorption wavelength to the absorbance A550 at a wavelength of 550 nm (absorbance Amax / absorbance A550) is preferably 20 to 500, more preferably 50 to 500, even more preferably 70 to 450, and particularly preferably 100 to 400. The infrared cut filter can be formed using a curable composition containing an infrared-absorbing colorant.

[0020] The infrared transmission filter is a filter that transmits at least a portion of infrared light. The infrared transmission filter is preferably a filter that blocks at least a portion of visible light and transmits at least a portion of infrared light. Examples of the infrared transmission filter include a filter that satisfies the spectral characteristics of a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1300 nm. The infrared transmission filter is preferably a filter that satisfies any one of the following spectral characteristics (1) to (5): (1): A filter that has a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 800 to 1500 nm. (2): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 750 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 900 to 1500 nm. (3): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 830 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1000 to 1500 nm. (4): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 950 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1100 to 1500 nm. (5): A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) in the wavelength range of 400 to 1050 nm, and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) in the wavelength range of 1200 to 1500 nm.

[0021] The curable composition of the present invention can also be used as a light-shielding film.

[0022] The solids concentration of the curable composition of the present invention is preferably 5 to 30% by mass. The lower limit is preferably 7.5% by mass or more, more preferably 10% by mass or more. The upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0023] The curable composition of the present invention exhibits high sensitivity when exposed to light with a wavelength of 150 to 300 nm. Therefore, the curable composition of the present invention is preferably used as a curable composition for exposure to light with a wavelength of 150 to 300 nm. Examples of light with a wavelength of 150 to 300 nm include KrF radiation (wavelength 248 nm) and ArF radiation (wavelength 193 nm), with KrF radiation (wavelength 248 nm) being preferred. The light with a wavelength of 150 to 300 nm is preferably excimer laser light with a wavelength of 150 to 300 nm.

[0024] Each component used in the curable composition of the present invention will be described below.

[0025] <<Photopolymerization initiator>> The curable composition of the present invention contains a photopolymerization initiator. The photopolymerization initiator is not particularly limited and can be appropriately selected from known photopolymerization initiators. For example, a compound that is photosensitive to light in the ultraviolet to visible region is preferred. The photopolymerization initiator is preferably a photoradical polymerization initiator.

[0026] Examples of the photopolymerization initiator include halogenated hydrocarbon derivatives (e.g., compounds having a triazine skeleton, compounds having an oxadiazole skeleton, etc.), acylphosphine compounds, hexaarylbiimidazole compounds, oxime compounds, organic peroxides, thio compounds, ketone compounds, aromatic onium salts, α-hydroxyketone compounds, α-aminoketone compounds, etc. From the viewpoint of exposure sensitivity, the photopolymerization initiator is preferably a trihalomethyltriazine compound, a benzyl dimethyl ketal compound, an α-hydroxyketone compound, an α-aminoketone compound, an acylphosphine compound, a phosphine oxide compound, a metallocene compound, an oxime compound, a hexaarylbiimidazole compound, an onium compound, a benzothiazole compound, a benzophenone compound, an acetophenone compound, a cyclopentadiene-benzene-iron complex, a halomethyloxadiazole compound, or a 3-aryl-substituted coumarin compound, more preferably a compound selected from an oxime compound, an α-hydroxyketone compound, an α-aminoketone compound, and an acylphosphine compound, and even more preferably an oxime compound.Examples of the photopolymerization initiator include the compounds described in paragraphs 0065 to 0111 of JP-A No. 2014-130173, the compounds described in Japanese Patent No. 6301489, and the compounds described in MATERIAL STAGE 37-60pp, vol. 19, No. peroxide-based photopolymerization initiators described in JP-A-2019-3, 2019, photopolymerization initiators described in WO 2018 / 221177, photopolymerization initiators described in WO 2018 / 110179, photopolymerization initiators described in JP-A-2019-043864, photopolymerization initiators described in JP-A-2019-044030, peroxide-based initiators described in JP-A-2019-167313, aminoacetophenone-based initiators having an oxazolidine group described in JP-A-2020-055992, Oxime-based photopolymerization initiators described in JP-A-0459, polymers described in JP-A-2020-172619, compounds represented by formula 1 described in WO 2020 / 152120, compounds described in JP-A-2021-181406, photopolymerization initiators described in JP-A-2022-013379, compounds represented by formula (1) described in JP-A-2022-015747, fluorine-containing fluorene oxime ester-based photoinitiators described in JP-T-2021-507058, Chinese Patent Application Publication No. 1107643 Initiators described in Patent Publication No. 67, initiators described in JP-T-2022-518535, initiators described in WO 2021 / 175855, compounds described in Taiwan Patent Application Publication No. 202200534, compounds described in JP-A-2022-078550, compounds described in Korean Patent Publication No. 10-2017-0087330, compounds described in WO 2022 / 075452, oxime ester compounds described in Chinese Patent Application Publication No. 110066225, Korean Patent Publication No. 10-2017-0087330, Examples of the photopolymerization initiator include compounds described in WO 2019 / 013112, compounds having a triarylamine or N-arylcarbazole skeleton described in paragraphs 0042 to 0062, oxime ester photopolymerization initiators described in Japanese Patent No. 7219378, photopolymerization initiators described in Korean Patent Publication No. 10-2021-0146174, photopolymerization initiators described in WO 2019 / 013112, and photopolymerization initiators described in JP 2023-033731 A.

[0027] Specific examples of hexaarylbiimidazole compounds include 2,2',4-tris(2-chlorophenyl)-5-(3,4-dimethoxyphenyl)-4,5-diphenyl-1,1'-biimidazole.

[0028] Commercially available α-hydroxyketone compounds include Omnirad 184, Omnirad 1173, Omnirad 2959, and Omnirad 127 (all manufactured by IGM Resins B.V.), and Irgacure 184, Irgacure 1173, Irgacure 2959, and Irgacure 127 (all manufactured by BASF). Commercially available α-aminoketone compounds include Omnirad 907, Omnirad 369, Omnirad 369E, Omnirad 379EG (all manufactured by IGM Resins B.V.), Irgacure 907, Irgacure 369, Irgacure 369E, Irgacure 379EG (all manufactured by BASF), etc. Commercially available acylphosphine compounds include Omnirad 819, Omnirad TPO (all manufactured by IGM Resins B.V.), Irgacure 819, Irgacure TPO (all manufactured by BASF), etc.

[0029] Examples of the oxime compound include the compounds described in paragraph 0142 of WO 2022 / 085485, the compounds described in Japanese Patent No. 5430746, the compounds described in Japanese Patent No. 5647738, the compounds represented by the general formula (1) of JP-A-2021-173858, and the compounds described in paragraphs 0022 to 0024, and the compounds represented by the general formula (1) of JP-A-2021-170089 and the compounds described in paragraphs 0117 to 0120. Specific examples of the oxime compound include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, 1-[4-(phenylthio)phenyl]-3-cyclohexyl-propane-1,2-dione-2-(O-acetyloxime), and the like. Commercially available products include Irgacure OXE01, Irgacure OXE02, Irgacure OXE03, Irgacure OXE04, Irgacure OXE05 (all manufactured by BASF), TR-PBG-301, TR-PBG-304, TR-PBG-305, TR-PBG-309, TR-PBG-3054, TR-PBG-3057, TR-PBG-314, TR-PBG-327, TR-PBG-345, TR-PBG-346, TR- Examples of the oxime compound include PBG-358, TR-PBG-365, TR-PBG-380, TR-PBG-610, TR-PBG-A, and TR-PBG-B (all manufactured by TRONLY Corporation), and ADEKA OPTOMER N-1919 (manufactured by ADEKA Corporation; photopolymerization initiator 2 described in JP 2012-014052 A). In addition, it is also preferable to use, as the oxime compound, a compound that is not colorable or a compound that is highly transparent and does not easily discolor. Commercially available products include ADEKA ARCLES NCI-730, NCI-831, NCI-831E, and NCI-930 (all manufactured by ADEKA Corporation).

[0030] As the photopolymerization initiator, an oxime compound having a fluorene ring, an oxime compound having a skeleton in which at least one benzene ring of a carbazole ring is replaced with a naphthalene ring, an oxime compound having a fluorine atom, an oxime compound having a nitro group, an oxime compound having a benzofuran skeleton, an oxime compound in which a substituent having a hydroxy group is bonded to a carbazole skeleton, or a compound described in paragraphs 0143 to 0149 of WO 2022 / 085485 can also be used.

[0031] As the photopolymerization initiator, a compound represented by formula (OX-1) can also be used.

[0032] In formula (OX-1), X １ａ represents a divalent linking group containing at least one ring selected from the group consisting of an aromatic ring and a heterocyclic ring; １ａ represents a hydrogen atom or an acyl group; R ２ａ represents an alkyl group or an aryl group; R ３ａ and R ４ａ each independently represents a hydrogen atom or an alkyl group; Alk １ and Alk ２ each independently represents an alkyl group; R ３ａ and R ４ａ may be bonded to form a ring, Alk １ and Alk ２ may be bonded to form a ring, and n represents 0 or 1.

[0033] X in formula (OX-1) １ａ Examples of the divalent linking group represented by include a divalent aromatic ring group, a divalent heterocyclic group, a divalent group in which two or more aromatic rings are bonded via a single bond or a linking group, a divalent group in which two or more heterocycles are bonded via a single bond or a linking group, and a divalent group in which an aromatic ring and a heterocycle are bonded via a single bond or a linking group. Examples of the linking group that bonds the above-mentioned aromatic rings, heterocyclic groups, or aromatic rings and heterocycles include -CH ２ -, -O-, -CO-, -S-, -NR ｘ - and groups combining these. ｘrepresents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heterocyclic group.

[0034] X in formula (OX-1) １ａ is preferably a group represented by any one of formulas (X-1) to (X-13), more preferably a group represented by formula (X-1), formula (X-2), formula (X-4), formula (X-6) or formula (X-8), and further preferably a group represented by formula (X-2) or formula (X-6).

[0035] In the formula R Ｘ１ ~R Ｘ９ each independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group, and * represents a bond.

[0036] R Ｘ１ ~R Ｘ９ The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heteroaryl group.

[0037] R Ｘ１ ~R Ｘ９ The number of carbon atoms in the alkenyl group represented by is preferably 2 to 15, and more preferably 2 to 10. The alkenyl group may be linear, branched, or cyclic. The alkenyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heteroaryl group.

[0038] R Ｘ１ ~R Ｘ９ The number of carbon atoms in the alkynyl group represented by is preferably 2 to 15, and more preferably 2 to 10. The alkynyl group may be linear, branched, or cyclic. The alkynyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, and a heteroaryl group.

[0039] R Ｘ１ ~R Ｘ９The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heteroaryl group.

[0040] R Ｘ１ ~R Ｘ９ The heteroaryl group represented by is preferably a 5-membered or 6-membered ring. The heteroatoms contained in the heteroaryl group are preferably oxygen atoms, nitrogen atoms, and sulfur atoms. The number of heteroatoms contained in the heteroaryl group is preferably 1 to 3. The heteroaryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and an aryl group.

[0041] R in formula (OX-1) １ａ represents a hydrogen atom or an acyl group, and is preferably an acyl group. １ａ The acyl group represented by is —C(O)—R １０１ａ It is preferable that R １０１ａ represents an aryl group or a heteroaryl group, and is preferably an aryl group.

[0042] R １０１ａ The number of carbon atoms in the aryl group represented by R is preferably 6 to 20, and more preferably 6 to 12. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, a heteroaryl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an arylamino group, and an acyl group. １０１ａ The aryl group represented by is preferably a phenyl group, a methylphenyl group or a naphthyl group, more preferably a methylphenyl group or a naphthyl group.

[0043] R １０１ａThe heteroaryl group represented by is preferably a 5- or 6-membered ring. The heteroatoms contained in the heteroaryl group are preferably oxygen, nitrogen, or sulfur atoms. The number of heteroatoms contained in the heteroaryl group is preferably 1 to 3. The heteroaryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an arylamino group, and an acyl group.

[0044] R １０１ａ is also preferably a group represented by any one of the above formulas (X-1) to (X-13). １０１ａ It is also preferable that the groups represented by formulas (X-1) to (X-13) further have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an arylamino group, and an acyl group.

[0045] R １０１ａ The aryl group and heteroaryl group represented by formula (Ar-1) may be a fused ring formed by condensing three or more rings. Examples of the fused ring aryl group and heteroaryl group formed by condensing three or more rings include groups represented by formulas (Ar-1) to (Ar-32) listed in the section on specific compounds described below.

[0046] R in formula (OX-1) ２ａ represents an alkyl group or an aryl group, and is preferably an alkyl group because the reactivity of the generated radical is high. ２ａ The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent, but is preferably an unsubstituted alkyl group. R ２ａThe alkyl group represented by R is preferably an unsubstituted linear or branched alkyl group, and more preferably an unsubstituted linear alkyl group. ２ａ The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6. The aryl group may have a substituent, but is preferably an unsubstituted aryl group.

[0047] R in formula (OX-1) ３ａ and R ４ａ R each independently represents a hydrogen atom or an alkyl group, and is preferably a hydrogen atom. ３ａ and R ４ａ The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent, but is preferably an unsubstituted alkyl group. R ３ａ and R ４ａ may be bonded to form a ring. The ring formed is preferably a 5- or 6-membered ring, and more preferably a 5- or 6-membered aliphatic hydrocarbon ring.

[0048] Alk of formula (OX-1) １ and Alk ２ each independently represents an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 15, more preferably 1 to 10, even more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent, but is preferably an unsubstituted alkyl group. Alk １ and Alk ２may be bonded to form a ring, and preferably form a ring. The ring formed is preferably a 5- or 6-membered ring, more preferably a 5- or 6-membered aliphatic hydrocarbon ring, and more preferably a cyclopentane ring or a cyclohexane ring.

[0049] In formula (OX-1), n ​​represents 0 or 1, and is preferably 0.

[0050] Specific examples of the compound represented by formula (OX-1) include the compounds described in paragraphs 0092 to 0096 of JP-A No. 2012-113104 and the compound described in paragraph 0041 of JP-A No. 2012-189997.

[0051] As the photopolymerization initiator, a compound represented by formula (OX-2) can also be used.

[0052]

[0053] In formula (OX-2), R １ｂ and R ２ｂ each independently represents a substituent, R ３ｂ ~R ７ｂ each independently represents a hydrogen atom or a substituent, Ar １ｂ represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent; n represents 0 or 1;

[0054] R １ｂ and R ２ｂ Examples of the substituent represented by include an alkyl group and an aryl group, and an alkyl group is preferred. The alkyl group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkenyl group, an alkynyl group, and a heteroaryl group. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, even more preferably 6 to 10 carbon atoms, and particularly preferably 6 carbon atoms. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heteroaryl group.

[0055] R ３ｂ ~R ７ｂ Examples of the substituent represented by R include a halogen atom, an alkyl group, and an aryl group. Examples of the alkyl group and the aryl group include those described above. ３ｂ ~R ７ｂ is preferably a hydrogen atom.

[0056] Ar １ｂ represents an aryl group which may have a substituent or a heteroaryl group which may have a substituent, Ar １ｂ is preferably an aryl group which may have a substituent. The number of carbon atoms in the aryl group is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6. Examples of the substituent include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, an alkylthio group, an arylthio group, a nitro group, and an acyl group, and an acyl group is preferred. Examples of the acyl group include the acyl groups described above, and -C(O)-R １０１ａ It is preferable that:

[0057] As the photopolymerization initiator, a compound represented by formula (OX-3) can also be used.

[0058]

[0059] In formula (OX-3), Ar １ｃ represents a (k+m+1)-valent aromatic ring group or a (k+m+1)-valent heterocyclic group; Ar ２ｃ represents a (k+2)-valent aromatic ring group or a (k+2)-valent heterocyclic group; R １ｃ ~R ３ｃ each independently represents a substituent; １ｃ is a single bond or CR １１ｃ R １２ｃ represents R １１ｃ and R １２ｃ each independently represents a hydrogen atom, an alkyl group, or an aryl group; １ｃ Ha-CH ２ represents -, -N-, -O- or -S-; k represents 0 or 1; m represents an integer of 0 to 4; and n represents 0 or 1.

[0060] R １ｃ and R ２ｃ Examples of the substituent represented by include an alkyl group and an aryl group, and an alkyl group is preferred. The alkyl group preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms. The alkyl group may be linear, branched, or cyclic. The alkyl group may have a substituent. Examples of the substituent include a halogen atom, an aryl group, an alkenyl group, an alkynyl group, and a heteroaryl group. The aryl group preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, even more preferably 6 to 10 carbon atoms, and particularly preferably 6 carbon atoms. The aryl group may have a substituent. Examples of the substituent include a halogen atom, an alkyl group, an alkenyl group, an alkynyl group, and a heteroaryl group. R ２ｃ is preferably an alkyl group having a branched or cyclic structure.

[0061] R ３ｃ Examples of the substituent represented by include a halogen atom, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, and an acyl group, and an acyl group is preferred. Examples of the acyl group include the acyl groups described above, and -C(O)-R １０１ａ It is preferable that:

[0062] L １ｃ is a single bond or CR １１ｃ R １２ｃ represents R １１ｃ and R １２ｃ R each independently represents a hydrogen atom, an alkyl group, or an aryl group. １１ｃ and R １２ｃ The alkyl group and aryl group in R １ｃ and R ２ｃ When k is 1, L １ｃ is preferably a single bond.

[0063] X １ｃ is -CH ２ It represents -, -N-, -O- or -S-, and is preferably -O- or -S-.

[0064] Ar１ｃ represents a (k+m+1)-valent aromatic ring group or a (k+m+1)-valent heterocyclic group, and is preferably a (k+m+1)-valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

[0065] Ar ２ｃ represents a (k+2)-valent aromatic ring group or a (k+2)-valent heterocyclic group, and is preferably a (k+2)-valent aromatic ring group. The aromatic ring group is preferably a benzene ring group or a naphthalene ring group, and more preferably a benzene ring group.

[0066] k represents 0 or 1, and is preferably 0. m represents an integer of 0 to 4, and is preferably 0 or 1, and more preferably 1. n represents 0 or 1, and is preferably 0.

[0067] The photopolymerization initiator is also preferably an oxime compound having an indole skeleton. The oxime compound having an indole skeleton is preferably a compound represented by formula (OX-2).

[0068] As the photopolymerization initiator, a ketoxime ester compound having an aryloxy group at the ortho position, represented by formula (OX-4), can also be suitably used. Examples of such compounds include the compounds described in Chinese Patent Application Publication No. 117342977.

[0069] In formula (OX-4), R １ｄ and R ２ｄ each independently represents an alkyl group, an aryl group, or a heterocyclic group; R ３ｄ , R ４ｄ , R ５ｄ , R ６ｄ are each independently a hydrogen atom, a halogen atom, CN, NO ２ , C.F. ３ ,R,OR,SR,SOR,SO ２R or NRR', R and R' each independently represent an alkyl group or an aryl group, and when R and R' are present at the same time, R and R' may be bonded to form a ring, and one or more -CH in the alkyl group or aryl group represented by R and R' ２ - may be independently substituted with -O-, -N-, -S-, -CO-, -COO-, -OCO- or a benzene ring; R ７ｄ , R ８ｄ and R ９ｄ each independently represents a hydrogen atom or a methyl group.

[0070] The photopolymerization initiator may also be a compound represented by formula (OX-5). Examples of such a compound include the compounds described in WO 2024 / 101219.

[0071] In formula (OX-5), R １ｅ ~R ｅ５ each independently represents a hydrocarbon group which may have a substituent; n represents an integer of 0 to 4.

[0072] Specific examples of oxime compounds that can be preferably used in the present invention are shown below, but the present invention is not limited to these.

[0073]

[0074]

[0075]

[0076]

[0077]

[0078] As the photopolymerization initiator, a bifunctional or trifunctional or higher functional photoradical polymerization initiator may be used. By using such a photoradical polymerization initiator, two or more radicals are generated from one molecule of the photoradical polymerization initiator, thereby obtaining good sensitivity. Furthermore, when a compound with an asymmetric structure is used, crystallinity is reduced and solubility in solvents is improved, making it less likely to precipitate over time, thereby improving the storage stability of the photosensitive composition. Specific examples of bifunctional or trifunctional or higher functional photoradical polymerization initiators include the compounds described in paragraph 0148 of WO 2022 / 065215.

[0079] The content of the photopolymerization initiator in the total solid content of the curable composition is preferably 1 to 10% by mass. The lower limit is preferably 1% by mass or more, and more preferably 2% by mass or more. The upper limit is preferably 10% by mass or less, and more preferably 8% by mass or less. The curable composition of the present invention may contain only one type of photopolymerization initiator, or may contain two or more types. When two or more types of photopolymerization initiators are contained, the total amount thereof is preferably within the above range.

[0080] <<Polymerizable Compound>> The curable composition of the present invention contains a polymerizable compound. Examples of the polymerizable compound include a compound having an ethylenically unsaturated bond-containing group. Examples of the ethylenically unsaturated bond-containing group include a vinyl group, a (meth)allyl group, and a (meth)acryloyl group. The polymerizable compound is preferably a radically polymerizable compound.

[0081] The polymerizable compound may be in any chemical form, such as a monomer, prepolymer, or oligomer, but is preferably a monomer. The molecular weight of the polymerizable compound is preferably 100 to 2500. The upper limit is preferably 2000 or less, more preferably 1500 or less. The lower limit is preferably 150 or more, more preferably 250 or more.

[0082] The ethylenically unsaturated bond-containing group value (hereinafter referred to as C═C value) of the polymerizable compound is preferably 2 to 14 mmol / g from the viewpoint of storage stability of the curable composition. The lower limit is preferably 3 mmol / g or more, more preferably 4 mmol / g or more, and even more preferably 5 mmol / g or more. The upper limit is preferably 12 mmol / g or less, more preferably 10 mmol / g or less, and even more preferably 8 mmol / g or less. The C═C value of the polymerizable compound is a value calculated by dividing the number of ethylenically unsaturated bond-containing groups contained in one molecule of the polymerizable compound by the molecular weight of the polymerizable compound.

[0083] The polymerizable compound is preferably a compound containing three or more ethylenically unsaturated bond-containing groups, more preferably a compound containing 3 to 15 ethylenically unsaturated bond-containing groups, and even more preferably a compound containing 3 to 6 ethylenically unsaturated bond-containing groups. Furthermore, the polymerizable compound is preferably a trifunctional to 15-functional (meth)acrylate compound, and more preferably a trifunctional to hexafunctional (meth)acrylate compound. Specific examples of the polymerizable compound include the compounds described in paragraphs 0075 to 0083 of WO 2022 / 065215 and the compounds described in Taiwan Patent Application Publication No. 201832008.

[0084] Preferred polymerizable compounds include dipentaerythritol tri(meth)acrylate (commercially available product: KAYARAD D-330, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol tetra(meth)acrylate (commercially available product: KAYARAD D-320, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate (commercially available product: KAYARAD D-310, manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (commercially available products: KAYARAD DPHA, manufactured by Nippon Kayaku Co., Ltd., and NK Ester A-DPH-12E, manufactured by Shin-Nakamura Chemical Co., Ltd.), and compounds having a structure in which the (meth)acryloyl group is bonded via an ethylene glycol and / or propylene glycol residue (e.g., SR454, SR499, commercially available from Sartomer). Examples of polymerizable compounds include diglycerin EO (ethylene oxide) modified (meth)acrylate (commercially available product: M-460, manufactured by Toagosei Co., Ltd.), pentaerythritol tetraacrylate (NK Ester A-TMMT, manufactured by Shin-Nakamura Chemical Co., Ltd.), and 1,6-hexanediol diacrylate (KAYARAD, manufactured by Nippon Kayaku Co., Ltd.). HDDA), RP-1040 (manufactured by Nippon Kayaku Co., Ltd.), Aronix TO-2349 (manufactured by Toagosei Co., Ltd.), NK Oligo UA-7200 (manufactured by Shin-Nakamura Chemical Co., Ltd.), DPHA-40H (manufactured by Nippon Kayaku Co., Ltd.), UA-306H, UA-306T, UA-306I, AH-600, T-600, AI-600, LINC-202UA (manufactured by Kyoeisha Chemical Co., Ltd.), 8UH-1006, 8UH-1012 (manufactured by Taisei Fine Chemical Co., Ltd.), Light Acrylate POB-A0 (manufactured by Kyoeisha Chemical Co., Ltd.), dendrimer structure or hyperbranched structure described in JP-A-2023-043479, and the like can also be used.

[0085] As the polymerizable compound, a polymerizable compound having an ethylene oxide repeating chain can also be used. According to this embodiment, the effects of the present invention are more pronounced. Examples of the polymerizable compound having an ethylene oxide repeating chain include a compound represented by formula (EO-1).

[0086] R in formula (EO-1) Ｅ１ represents a hydrogen atom or a methyl group.

[0087] L in formula (EO-1) Ｅ１ represents an m-valent linking group. Ｅ１ The m-valent linking group represented by is a hydrocarbon group, a heterocyclic group, —O—, —S—, —NR Ａ１ -, -CO-, -COO-, -OCO-, -SO ２ - and groups formed by combining two or more of these groups. Ａ１ represents a hydrogen atom, an alkyl group, or an aryl group, with a hydrogen atom being preferred. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be cyclic or acyclic. The acyclic aliphatic hydrocarbon group may be a straight-chain aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have a substituent or may not have a substituent. The cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be a monocyclic ring or a fused ring. The heterocyclic group may be a monocyclic ring or a fused ring. The heterocyclic group is preferably a 5- or 6-membered ring. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Examples of heteroatoms constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom.

[0088] In formula (EO-1), n ​​represents an integer of 1 to 20, and m represents an integer of 2 to 10. n is preferably an integer of 1 to 15, and more preferably an integer of 1 to 10. m is preferably an integer of 2 to 8, and more preferably an integer of 2 to 6.

[0089] As the polymerizable compound, a polymerizable compound having a fluorene skeleton can also be used. The polymerizable compound having a fluorene skeleton is preferably a bifunctional polymerizable compound. Examples of the polymerizable compound having a fluorene skeleton include compounds having a partial structure represented by the following formula (Fr):

[0090] In the formula, * represents a bond, and R ｆ１ and R ｆ２ each independently represents a substituent, and m and n each independently represent an integer of 0 to 5. When m is 2 or more, m R ｆ１ may be the same or different, and m R ｆ１ Two of the R ｆ１ When n is 2 or more, n R ｆ２ may be the same or different, and n R ｆ２ Two of the R ｆ２ They may be bonded to each other to form a ring. ｆ１ and R ｆ２ The substituent represented by is a halogen atom, a cyano group, a nitro group, an alkyl group, an aryl group, a heteroaryl group, -OR ｆ１１ , -COR ｆ１２ , -COOR ｆ１３ , -OCOR ｆ１４ , -NR ｆ１５ R ｆ１６ , -NHCOR ｆ１７ , -CONR ｆ１８ R ｆ１９ , -NHCONR ｆ２０ R ｆ２１ , -NHCOOR ｆ２２ , -SR ｆ２３ , -SO ２ R ｆ２４ , -SO ２ OR ｆ２５ , -NHSO ２ R ｆ２６ or -SO ２ NR ｆ２７ R ｆ２８ Examples include: R ｆ１１ ~R ｆ２８ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group.

[0091] Specific examples of polymerizable compounds having a fluorene skeleton include compounds having the following structure: Furthermore, commercially available polymerizable compounds having a fluorene skeleton include OGSOL EA-0200 and EA-0300 (manufactured by Osaka Gas Chemicals Co., Ltd., (meth)acrylate monomers having a fluorene skeleton).

[0092] The content of the polymerizable compound in the total solid content of the curable composition is preferably 1 to 30% by mass. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 10% by mass or less. The lower limit is preferably 3% by mass or more, and more preferably 5% by mass or more. The curable composition of the present invention may contain only one type of polymerizable compound, or may contain two or more types. When two or more types of polymerizable compounds are contained, the total amount thereof is preferably within the above range.

[0093] <<Specific Compound (Compound Represented by Formula (1))>> The curable composition of the present invention contains a compound represented by formula (1) (hereinafter also referred to as specific compound).

[0094] R in formula (1) １ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group, and is preferably an aryl group or an acyl group, more preferably an aryl group, and even more preferably an aryl group having an acyl group as a substituent, because this increases the absorbance at wavelengths of 150 to 300 nm and can further enhance the sensitivity to light at wavelengths of 150 to 300 nm. The acyl group is represented by the following —C(O)—R １０１ It is preferable that:

[0095] R in formula (1) １ The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear.

[0096] R in formula (1)１ The aryl group represented by the formula (I) preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, even more preferably 6 to 10 carbon atoms, and particularly preferably 6 or 7 carbon atoms.

[0097] R in formula (1) １ The number of carbon atoms constituting the ring of the heteroaryl group represented by is preferably 1 to 15, more preferably 1 to 10. Types of heteroatoms constituting the ring of the heteroaryl group include a nitrogen atom, an oxygen atom, and a sulfur atom. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3, more preferably 1 or 2. The heteroaryl group may be a monocyclic ring or a condensed ring.

[0098] R in formula (1) １ The acyl group represented by is —C(O)—R １０１ It is preferable that R １０１ represents an alkyl group, an aryl group, or a heteroaryl group, preferably an aryl group or a heteroaryl group, and more preferably an aryl group. １０１ The number of carbon atoms in the alkyl group represented by R is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic. １０１ The number of carbon atoms in the aryl group represented by R is preferably 6 to 20, more preferably 6 to 12. The aryl group may have a substituent. １０１ The number of carbon atoms constituting the ring of the heteroaryl group represented by is preferably 1 to 15, more preferably 1 to 10. The types of heteroatoms constituting the ring of the heteroaryl group include nitrogen atoms, oxygen atoms, and sulfur atoms. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. The heteroaryl group may be a monocyclic ring or a condensed ring. Examples of the heteroaryl group include a furan ring group, a benzofuran ring group, a thiophene ring group, and a benzothiophene ring group. In addition, R １０１ The aryl group and heteroaryl group represented by the formula (I) may be a fused ring formed by condensing three or more rings. Examples of the fused ring aryl group and heteroaryl group formed by condensing three or more rings include the groups shown below.

[0099]

[0100] In the above formula, * represents a bond, R ａ１ ~R ａ３２ each independently represents an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an arylamino group, a heteroaryloxy group, a heteroarylthio group, a heteroarylamino group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, a hydroxy group, a carboxy group, or a halogen atom; R ａｒ１ ~R ａｒ２５ each independently represents a hydrogen atom, an alkyl group, or an aryl group; and k1 to k32 each independently represent an integer of 0 to 4.

[0101] R in formula (1) １ The alkylsulfonyl group represented by the formula (I) preferably has 1 to 15 carbon atoms, and more preferably 1 to 10 carbon atoms.

[0102] R in formula (1) １ The arylsulfonyl group represented by the formula (I) preferably has 6 to 20 carbon atoms, more preferably 6 to 12 carbon atoms, still more preferably 6 to 10 carbon atoms, and particularly preferably 6 carbon atoms.

[0103] R １ alkyl groups, aryl groups, heteroaryl groups, acyl groups, alkylsulfonyl groups and arylsulfonyl groups represented by R １０１ The alkyl group, aryl group, and heteroaryl group represented by may have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an arylamino group, a heteroaryloxy group, a heteroarylthio group, a heteroarylamino group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, a hydroxy group, a carboxy group, and a halogen atom, and an acyl group, a nitro group, an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, or an arylamino group is preferred.

[0104] R in formula (1) ２ represents an alkyl group, an aryl group, or a heteroaryl group.

[0105] R ２ The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, and more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic, but is preferably branched or cyclic, and more preferably cyclic. The alkyl group may have a substituent. Examples of the substituent include an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an arylamino group, a heteroaryloxy group, a heteroarylthio group, a heteroarylamino group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, a hydroxy group, a carboxy group, and a halogen atom.

[0106] R ２ The aryl group and heteroaryl group represented by R １ Examples of the aryl and heteroaryl groups represented by R ２ The aryl group and heteroaryl group represented by may have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an arylamino group, a heteroaryloxy group, a heteroarylthio group, a heteroarylamino group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, a hydroxy group, a carboxy group, and a halogen atom.

[0107] R in formula (1) ２ is preferably an alkyl group, more preferably a branched or cyclic alkyl group, and even more preferably a cyclic alkyl group, because this improves the solvent solubility of the specific compound and allows it to be dispersed more uniformly in the curable composition.

[0108] R in formula (1) ２ is preferably a group represented by formula (R-2). In formula (R-2), * represents a bond, ｒ１ represents a single bond or an alkylene group; ｒ１ and R ｒ２ each independently represents an alkyl group; R ｒ１ and R ｒ２ may be bonded to each other to form a ring.

[0109] L in formula (R-2) ｒ１ represents a single bond or an alkylene group, preferably an alkylene group. The alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.

[0110] R in formula (R-2) ｒ１ and R ｒ２ The number of carbon atoms in the alkyl group represented by is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The alkyl group may be linear, branched, or cyclic. ｒ１ and R ｒ２ may be bonded to each other to form a ring. The ring formed is preferably a 3- to 6-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 5-membered ring.

[0111] R in formula (1) ２ is particularly preferably a group represented by formula (R-2a). In formula (R-2a), * represents a bond, ｒ３ and R ｒ４ each independently represents a hydrogen atom or an alkyl group; ｒ２ represents a single bond or an alkylene group; ｒ３ is -(CR Ｌ１ R Ｌ２ ) ｐ represents -, and R Ｌ１ and R Ｌ２ each independently represents a hydrogen atom or an alkyl group, and p represents an integer of 1 to 5.

[0112] L in formula (R-2a) ｒ２represents a single bond or an alkylene group, preferably an alkylene group. The alkylene group preferably has 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, even more preferably 1 to 3 carbon atoms, and particularly preferably 1 or 2 carbon atoms.

[0113] R ｒ３ , R ｒ４ , R Ｌ１ and R Ｌ２ The number of carbon atoms in the alkyl group represented by R is preferably 1 to 6, and more preferably 1 to 3. The alkyl group is preferably linear or branched. ｒ３ , R ｒ４ , R Ｌ１ and R Ｌ２ is preferably a hydrogen atom.

[0114] p represents an integer of 1 to 5, preferably an integer of 2 to 4, more preferably 3 or 4, and even more preferably 3.

[0115] R ２ Specific examples of include an isopropyl group, an isopropylmethyl group, an isopropylethyl group, a cyclopentyl group, a cyclopentylethyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylethyl group, a cyclohexylmethyl group, and groups represented by formulas (Y-1) to (Y-32) shown below, of which an isopropyl group, an isopropylmethyl group, an isopropylethyl group, a cyclopentyl group, a cyclopentylethyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylethyl group, and a cyclohexylmethyl group are preferred. In the following formulas, * represents a bond.

[0116] R in formula (1) ３ ~R ７ R each independently represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group. ３ ~R ７ Examples of the monovalent organic group represented by R include an alkyl group, an alkenyl group, and an aryl group. ４ ~R ７Adjacent groups among R in formula (1) may be bonded to each other to form a ring. The formed ring is preferably a 5-membered ring or a 6-membered ring. ３ ~R ７ is preferably a hydrogen atom.

[0117] The specific compound is preferably a compound that does not have an oxime group.

[0118] The specific compound is preferably a compound represented by formula (2), more preferably a compound represented by formula (2a). The compound represented by formula (2a) is also the compound of the present invention. In formula (2), R ２１ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group; L ２１ represents a single bond or an alkylene group; R ２２ａ and R ２２ｂ each independently represents an alkyl group, R ２２ａ and R ２２ｂ may be bonded to form a ring, R ２３ ~R ２７ each independently represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; R ２４ ~R ２７ Adjacent groups among these may be bonded to form a ring.

[0119] In formula (2a), R ２１ａ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group; L ２１ａ represents an alkylene group having 1 to 4 carbon atoms; R ２２Ｌａ and R ２２Ｌｂ each independently represents an alkyl group, R ２２Ｌａ and R ２２Ｌｂ may be bonded to form a ring, R ２３ａ ~R ２７ａ each independently represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; R ２４ａ ~R ２７ａAdjacent groups among these may be bonded to form a ring.

[0120] R in formula (2) ２１ and R in formula (2a) ２１ａ is R in formula (1). １ The same definition and preferred range are also true. ２３ ~R ２７ and R in formula (2a) ２３ａ ~R ２７ａ is R in formula (1). ３ ~R ７ The same applies to the preferred range.

[0121] L in formula (2) ２１ The number of carbon atoms in the alkylene group represented by is preferably 1 to 6, more preferably 1 to 4, even more preferably 1 to 3, and particularly preferably 1 or 2. ２１ａ The alkylene group represented by has 1 to 4 carbon atoms, preferably 1 to 3 carbon atoms, and more preferably 1 or 2 carbon atoms.

[0122] R in formula (2) ２２ａ and R ２２ｂ and R in formula (2a) ２２Ｌａ and R ２２Ｌｂ The number of carbon atoms in the alkyl group represented by is preferably 1 to 10, more preferably 1 to 6, and even more preferably 1 to 4. The alkyl group may be linear, branched, or cyclic. ２２ａ and R ２２ｂ may be bonded to form a ring. ２２Ｌａ and R ２２Ｌｂ may be bonded to form a ring. The ring formed is preferably a 3- to 6-membered ring, more preferably a 5- or 6-membered ring, and even more preferably a 5-membered ring.

[0123] The specific compound is preferably a compound represented by formula (3). In formula (3), R ３１ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group; L３１ represents a single bond or an alkylene group having 1 to 4 carbon atoms; L ３２ Ha-(CR Ｌ１ R Ｌ２ ) ｐ represents -, and R Ｌ１ and R Ｌ２ each independently represents a hydrogen atom or an alkyl group, p represents an integer of 1 to 5, ３２ａ and R ３２ｂ each independently represents a hydrogen atom or an alkyl group; R ３３ ~R ３７ each independently represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; R ３４ ~R ３７ Adjacent groups among these may be bonded to form a ring.

[0124] R in formula (3) ３１ is R in formula (1). １ The same definition and preferred range are also true. ３３ ~R ３７ is R in formula (1). ３ ~R ７ The same applies to the preferred range.

[0125] L in formula (3) ３１ represents a single bond or an alkylene group having 1 to 4 carbon atoms, preferably an alkylene group having 1 to 4 carbon atoms, more preferably an alkylene group having 1 to 3 carbon atoms, and even more preferably an alkylene group having 1 or 2 carbon atoms.

[0126] R ３２ａ , R ３２ｂ , R Ｌ１ and R Ｌ２ The number of carbon atoms in the alkyl group represented by R is preferably 1 to 6, and more preferably 1 to 3. The alkyl group is preferably linear or branched. ３２ａ , R ３２ｂ , R Ｌ１ and R Ｌ２ is preferably a hydrogen atom.

[0127] p represents an integer of 1 to 5, preferably an integer of 2 to 4, more preferably 3 or 4, and even more preferably 3.

[0128] The specific compound is preferably a compound represented by formula (4). In formula (4), R ４１ represents a hydrogen atom, a halogen atom, a nitro group or an acyl group; R ４２ represents an alkyl group, an aryl group, or a halogen atom; R ４３ ~R ４７ each independently represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; R ４４ ~R ４７ Adjacent groups among these may be bonded to form a ring, and m represents an integer of 0 to 4.

[0129] R in formula (4) ４３ ~R ４７ is R in formula (1). ３ ~R ７ The same applies to the preferred range.

[0130] R in formula (4) ４１ represents a hydrogen atom, a halogen atom, a nitro group, or an acyl group, and is preferably an acyl group. １ The acyl group represented by —C(O)—R １０１ The preferred ranges are also the same.

[0131] R in formula (4) ４２The number of carbon atoms in the alkyl group represented by is preferably 1 to 15, more preferably 1 to 10. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent. Examples of the substituent include an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an arylamino group, a heteroaryloxy group, a heteroarylthio group, a heteroarylamino group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, a hydroxy group, a carboxy group, and a halogen atom. R in formula (4) ４２ The number of carbon atoms in the aryl group represented by is preferably 6 to 20, more preferably 6 to 12, still more preferably 6 to 10, and particularly preferably 6. The aryl group may have a substituent. Examples of the substituent include an alkyl group, an alkenyl group, an aryl group, a heteroaryl group, an alkoxy group, an alkylthio group, an alkylamino group, an aryloxy group, an arylthio group, an arylamino group, a heteroaryloxy group, a heteroarylthio group, a heteroarylamino group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, a hydroxy group, a carboxy group, and a halogen atom. R in formula (4) ４２ The halogen atom represented by the formula (I) includes a chlorine atom, a fluorine atom, a bromine atom and an iodine atom.

[0132] The specific compound can be preferably used as a photosensitizer.

[0133] The specific compound can be synthesized by introducing a carbonyl group into an indole ring. The introduction of the carbonyl group into the indole ring can be achieved by a Friedel-Crafts type reaction using a Lewis acid or a Bronsted acid, or by an exchange anhydride method using a Lewis acid or a Bronsted acid. There are no particular limitations on the method, as long as it involves electrophilic addition of an acyl cation to an indole ring. Alternatively, a method of coupling a compound having an indole skeleton containing a halogen atom with a carboxylic acid, a carboxylic acid halide, a carboxylic acid anhydride, an aldehyde, or a dicarbonyl compound in the presence of a transition catalyst can also be suitably used.

[0134] For example, the specific compound can be prepared by reacting a raw material indole compound with a Lewis acid (AlCl ３ , SnCl ４ , B.F. ３ , BCl ３ , BBr ３ , AlBr ３ , FeCl ３ , FeBr ３ , GaCl ３ , SbCl ３ , SbBr ３ , InCl ３ , InBr ３ , SnCl ４ , SnBr ４ , AsCl ５ , ZnCl ２ , ZnBr ２ , CdCl ２ , HgCl ２ The indole derivative can be synthesized by carrying out a Friedel-Crafts reaction with an acid chloride or an acid anhydride (including mixed acid anhydrides) in the presence of an indole derivative (e.g., a carboxylic acid). The free NH of the indole skeleton may or may not be protected as appropriate. When protected, the protecting group is preferably an acyl group, an alkylsulfonyl group, or an arylsulfonyl group.

[0135] In the synthesis of a specific compound, in addition to Lewis acids, common Bronsted acids can be used as acids that can be used to introduce a carbonyl group into an indole ring. For example, strong acids such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, acetic acid, trifluoroacetic acid, methanesulfonic acid, trifluoromethanesulfonic acid, p-toluenesulfonic acid, and camphorsulfonic acid can be preferably used. Trifluoroacetic anhydride can also be used. Multiple acids may be used, but the pKa of the strongest acid used is preferably less than 0, more preferably less than -2. Carbonyl sources that can be used to introduce a carbonyl group include carboxylic acids, carboxylic anhydrides, and carboxylic acid halides. Examples of Friedel-Crafts type reactions include AlCl ３ or SnCl ４Examples include a combination of a carboxylic acid halide or a carboxylic acid anhydride with a carboxylic acid. Examples of the acid exchange anhydride method include a combination of a carboxylic acid in the presence of trifluoroacetic acid and methanesulfonic acid. The reaction temperature is not particularly limited, but can be between -20°C and 130°C, preferably between -10°C and 100°C, and more preferably between 0°C and 80°C, from the viewpoint of reducing by-products and suppressing coloration. The solvent that can be used in the synthesis of the specific compound is not particularly limited, and examples include aromatic solvents, hydrocarbon solvents, ether solvents, ester solvents, ketone solvents, halogenated solvents, amide solvents, urea solvents, carbonate solvents, and alcohol solvents. Solvents that do not inactivate the acid are preferred, and those that can simultaneously dissolve the acid uniformly are also preferred. Aromatic solvents, hydrocarbon solvents, ether solvents, and halogenated solvents are most preferred. From the viewpoint of reducing the electrophilicity and increasing the electrophilicity of the indole skeleton of the target raw material, it is more preferred that the aromatic solvent contains an electron-withdrawing group on the aromatic ring. Examples of such electron-withdrawing groups include halogen atoms (F, Cl, Br, I), nitro groups, cyano groups, and carbonyl groups. Two or more electron-withdrawing groups may be present. Examples include chlorobenzene, o-dichlorobenzene, m-dichlorobenzene, p-dichlorobenzene, trichlorobenzene, fluorobenzene, bromobenzene, nitrobenzene, cyanobenzene, and acetophenone. A solvent need not be used.

[0136] The specific compound can also be synthesized by referring to the method described in the following document: Organic & Biomolecular Chemistry Vol. 18 Issue 29, (2020), 5625-5638; Bioorganic & Medicinal Chemistry (2013), 21(24), 8019-8032 using methanesulfonic acid and diphosphorus pentoxide; Organic & Biomolecular Chemistry (2011), 9(15), 5431-5435 using methanesulfonic acid; Journal of the American Chemical Society (2022), 144(1), 137-144 using a combination of trifluoroacetic acid and trifluoroacetic anhydride; A method described in Tetrahedron Letters 59 (2018) 869, which combines trifluoroacetic acid, trifluoroacetic anhydride, and methanesulfonic acid; and a method described in ORGANIC LETTERS 2001 Vol. 3, No. 7 1005-1007, which selectively acylates the 3-position of indole using SnCl as a Lewis acid.

[0137] A general synthesis scheme for the specific compound is shown below, but the synthesis method for the specific compound is not limited to the following.

[0138] (General synthesis scheme using Lewis acid)

[0139] (General synthesis scheme using Bronsted acid)

[0140] In the above formula, Rx1 represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an acyl group, an alkylsulfonyl group, or an arylsulfonyl group; Rx2 represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; and Rx3 represents an alkyl group, an aryl group, or a heteroaryl group.

[0141] The molecular weight of the specific compound is preferably 200 to 2000. The upper limit is preferably 1000 or less, more preferably 900 or less. The lower limit is preferably 300 or more, more preferably 400 or more.

[0142] From the viewpoint of sensitivity, the molar absorption coefficient of the specific compound at a wavelength of 248 nm is 5000 L mol －１ ・cm －１ More than 10,000 L mol is preferable. －１ ・cm －１ More preferably, 20,000 L mol or more －１ ・cm －１ More preferably, 30,000 L mol or more －１ ・cm －１ The upper limit of the molar absorption coefficient at a wavelength of 248 nm is not particularly limited, but is preferably 200,000 L mol －１ ・cm －１ It is preferable that the specific compound has a long-wavelength absorption end (a molar absorption coefficient of 100 L mol －１ ・cm －１ The longest wavelength (the wavelength at which the absorption peak is shorter than the longest wavelength) is preferably 450 nm or less, more preferably 400 nm or less, and even more preferably 380 nm or less. When the long wavelength end of absorption is in the above-mentioned range, yellow light fogging is prevented and the light stability during synthesis is excellent. Furthermore, when the specific compound is applied to an optical filter such as a color filter, the color reproducibility is good because the specific compound does not exhibit yellow color.

[0143] The molar absorption coefficient of a specific compound is measured by the following method: 12.5 mg of the specific compound is weighed out and placed in a 100 mL volumetric flask. Acetonitrile is added to this and completely dissolved. 2 mL of this solution is taken with a volumetric pipette and made up to a 25 mL volumetric flask. This is the measurement sample. The measurement sample is placed in a 5 mL quartz glass cell, 1 cm square, and the absorbance is measured in air to calculate the molar absorption coefficient. Examples of measurement devices include an ultraviolet-visible-near-infrared spectrophotometer (UH4150, manufactured by Hitachi High-Tech Corporation).

[0144] The impurities that may be contained in the specific compound are described below. The content of water contained in the specific compound is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the specific compound. The lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass. The content of organic solvent contained in the specific compound is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the specific compound. The lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass. The content of organic acid and organic acid anhydride contained in the specific compound is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, relative to 100 parts by mass of the specific compound. The lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass. Examples of organic acids include formic acid, acetic acid, propionic acid, pivalic acid, succinic acid, phthalic acid, and benzoic acid. Examples of organic acid anhydrides include anhydrides of these acids. The content of the organic base contained in the specific compound is preferably 10 parts by mass or less, more preferably 5 parts by mass or less, even more preferably 3 parts by mass or less, and particularly preferably 1 part by mass or less, per 100 parts by mass of the specific compound. The lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass. Examples of organic bases include triethylamine, dimethylamine, diethylamine, pyridine, piperidine, pyrrolidine, morpholine, and amines used in producing the specific compound.The content of halogen contained in the specific compound is preferably 5 parts by mass or less, more preferably 3 parts by mass or less, and even more preferably 1 part by mass or less, per 100 parts by mass of the specific compound. The lower limit can be 0 parts by mass, 0.0001 parts by mass, 0.001 parts by mass, or 0.01 parts by mass. Examples of halogen include Cl, Br, F, and I, and may be organic compounds containing these halogen atoms. Ions of these halogens may also be used. The content of residual metal contained in the specific compound is preferably 0.1 parts by mass or less, more preferably 0.01 parts by mass or less, even more preferably 0.001 parts by mass or less, even more preferably less than 0.0001 parts by mass, and particularly preferably below the detection limit, per 100 parts by mass of the specific compound. The type of residual metal is not particularly limited, but examples include Li, Na, Mg, Al, K, Ca, Cr, Mn, Fe, Co, Ni, Cu, Zn, Cd, Pb, Ti, V, As, Ag, Sn, Ba, W, Au, and Zr.

[0145] Specific examples of the specific compound include compounds (A-1) to (A-80) described in the examples below.

[0146] The content of the specific compound in the total solid content of the curable composition is preferably 0.0001 to 20% by mass. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit is preferably 0.001% by mass or more, more preferably 0.01% by mass or more.

[0147] The curable composition preferably contains 0.01 to 500 parts by mass of the specific compound per 100 parts by mass of the photopolymerization initiator. The upper limit is preferably 300 parts by mass or less, more preferably 150 parts by mass or less, even more preferably 100 parts by mass or less, and particularly preferably 50 parts by mass or less. The lower limit is preferably 0.1 parts by mass or more, more preferably 0.5 parts by mass or more.

[0148] The curable composition of the present invention may contain only one specific compound or two or more specific compounds. When two or more specific compounds are contained, the total amount thereof is preferably within the above range.

[0149] <<Resin>> The curable composition of the present invention preferably contains a resin. The resin is blended, for example, for the purpose of dispersing pigments and the like in the curable composition or for use as a binder. Note that resins used primarily to disperse pigments and the like in the curable composition are also referred to as dispersants. However, these uses of resins are merely examples, and resins can also be used for purposes other than these uses.

[0150] The weight average molecular weight (Mw) of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.

[0151] Examples of resins include (meth)acrylic resins, epoxy resins, (meth)acrylamide resins, ene-thiol resins, polycarbonate resins, polyether resins, polyarylate resins, polysulfone resins, polyethersulfone resins, polyphenylene resins, polyarylene ether phosphine oxide resins, polyimide resins, polyamic acid resins (polyimide precursors), polyamideimide resins, polyolefin resins, cyclic olefin resins, polyester resins, styrene resins, and siloxane resins. Further, examples of the resin include the resins described in paragraphs 0091 to 0099 of WO 2022 / 065215, the blocked polyisocyanate resins described in JP 2016-222891 A, the resins described in JP 2020-122052 A, the resins described in JP 2020-111656 A, the resins described in JP 2020-139021 A, the resins described in JP 2017-138503 A containing a structural unit having a ring structure in the main chain and a structural unit having a biphenyl group in the side chain, the resins described in paragraphs 0199 to 0233 of JP 2020-186373 A, the alkali-soluble resins described in JP 2020-186325 A, and Korean Patent Publication No. 10-2020-007 Resins represented by formula 1 described in Patent Publication No. 8339, copolymers containing epoxy groups and acid groups described in WO 2022 / 030445, resins described in JP 2018-135514 A, copolymers described in JP 2020-041046 A, resins described in JP 2023-033156 A, resins described in JP 2023-030386 A, resins described in JP 2023-027753 A, crosslinkable group-containing negative photosensitive polyamic acid resins described in JP 5-040340 and JP 2021-131543 A, crosslinkable group-containing negative photosensitive polyimide resins described in JP 2022-135427 and JP 2023-166413 A can also be used.

[0152] The resin to be used is preferably a resin having an acid group, such as a carboxy group, a phosphate group, a sulfo group, or a phenolic hydroxy group.

[0153] The acid value of the resin having acid groups is preferably 30 to 500 mgKOH / g. The lower limit is preferably 40 mgKOH / g or more, and more preferably 50 mgKOH / g or more. The upper limit is preferably 400 mgKOH / g or less, more preferably 300 mgKOH / g or less, and even more preferably 200 mgKOH / g or less. The weight average molecular weight (Mw) of the resin having acid groups is preferably 5,000 to 100,000, and more preferably 5,000 to 50,000. The number average molecular weight (Mn) of the resin having acid groups is preferably 1,000 to 20,000.

[0154] The resin having an acid group preferably contains a repeating unit having an acid group on a side chain, and more preferably contains 5 to 70 mol% of the repeating units having an acid group on a side chain based on all repeating units of the resin. The upper limit of the content of repeating units having an acid group on a side chain is preferably 50 mol% or less, more preferably 30 mol% or less. The lower limit of the content of repeating units having an acid group on a side chain is preferably 10 mol% or more, more preferably 20 mol% or more.

[0155] For resins having acid groups, please refer to the descriptions in paragraphs

[0558] to

[0571] of JP 2012-208494 A (corresponding to paragraphs

[0685] to

[0700] of U.S. Patent Application Publication No. 2012 / 0235099 A) and paragraphs

[0076] to

[0099] of JP 2012-198408 A, the contents of which are incorporated herein by reference. Alternatively, commercially available resins having acid groups can be used. There are no particular limitations on the method for introducing acid groups into the resin, and examples include the method described in Japanese Patent No. 6,349,629 A. Furthermore, examples of methods for introducing acid groups into the resin include a method in which an acid anhydride is reacted with a hydroxy group generated by a ring-opening reaction of an epoxy group to introduce the acid group.

[0156] The curable composition of the present invention also preferably contains a resin having a basic group. The resin having a basic group is preferably a resin containing a repeating unit having a basic group in a side chain, more preferably a copolymer having a repeating unit having a basic group in a side chain and a repeating unit not containing a basic group, and even more preferably a block copolymer having a repeating unit having a basic group in a side chain and a repeating unit not containing a basic group. The resin having a basic group can also be used as a dispersant. The amine value of the resin having a basic group is preferably 5 to 300 mgKOH / g. The lower limit is preferably 10 mgKOH / g or more, more preferably 20 mgKOH / g or more. The upper limit is preferably 200 mgKOH / g or less, more preferably 100 mgKOH / g or less.

[0157] Commercially available resins having basic groups include DISPERBYK-161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, and BYK-LPN6919 (all manufactured by BYK-Chemie), and Solsperse 112. 00, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 7100 (all manufactured by The Lubrizol Group, Japan), Efka PX 4300, 4330, 4046, 4060, 4080 (all manufactured by BASF), and the like. In addition, the resin having a basic group may be the block copolymer (B) described in paragraphs 0063 to 0112 of JP-A-2014-219665, the block copolymer A1 described in paragraphs 0046 to 0076 of JP-A-2018-156021, or the vinyl resin having a basic group described in paragraphs 0150 to 0153 of JP-A-2019-184763, the contents of which are incorporated herein by reference.

[0158] The curable composition of the present invention also preferably contains both a resin having an acid group and a resin having a basic group. According to this embodiment, the storage stability of the curable composition can be further improved. When a resin having an acid group and a resin having a basic group are used in combination, the content of the resin having a basic group is preferably 20 to 500 parts by mass, more preferably 30 to 300 parts by mass, and even more preferably 50 to 200 parts by mass per 100 parts by mass of the resin having an acid group.

[0159] It is also preferable to use a resin having an aromatic carboxy group as the resin. In a resin having an aromatic carboxy group, the aromatic carboxy group may be contained in the main chain of the repeating unit or may be contained in a side chain of the repeating unit. It is preferable that the aromatic carboxy group is contained in the main chain of the repeating unit. In this specification, an aromatic carboxy group refers to a group having a structure in which one or more carboxy groups are bonded to an aromatic ring. In the aromatic carboxy group, the number of carboxy groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2. Examples of resins having an aromatic carboxy group include the resins described in paragraphs 0082 to 0107 of WO 2021 / 166858.

[0160] It is also preferable to use a resin having a crosslinkable group as the resin. Examples of the crosslinkable group include a (meth)acryloyl group, an epoxy group, and an oxetanyl group. When a resin having a crosslinkable group is used, the content of the resin having a crosslinkable group in the resin contained in the curable composition is preferably 30% by mass or more, more preferably 50% by mass or more, and even more preferably 70% by mass or more.

[0161] As the resin, a polyimide resin or a polyamic acid resin containing a repeating unit represented by formula (P-1) or formula (P-2) can also be used. In formulas (P-1) and (P-2), Xp represents a 4+n-valent linking group, and the 4+n-valent linking group is an aliphatic group having 6 to 50 carbon atoms, an aromatic group having 6 to 50 carbon atoms, or a group in which a plurality of these groups are bonded via a single bond or a linking group, and the linking group is -O-, -S-, -S=O-, -S(=O) ２ -, -CR Ｐ１ R Ｐ２ -, -(C=O)-, -C(=O)O-, -C(=O)NH-, a heterocyclic group, or a group combining two or more of these, Ｐ１ and R Ｐ２ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a trifluoromethyl group; R Ｐ１ and R Ｐ２ may be linked to each other to form a ring; Yp represents a 2+m-valent linking group, and the 2+m-valent linking group is an aliphatic group having 6 to 50 carbon atoms, an aromatic group having 6 to 50 carbon atoms, or a group in which a plurality of these groups are linked via a single bond or a linking group, and the linking group is -O-, -S-, -S=O-, -S(=O) ２ -, -CR Ｐ１ R Ｐ２ -, -(C=O)-, -C(=O)O-, -C(=O)NH-, a heterocyclic group, or a group combining two or more of these, Ｐ１ and R Ｐ２ each independently represents a hydrogen atom, an alkyl group, an aryl group, or a trifluoromethyl group; R Ｐ１ and R Ｐ２ may be linked to each other to form a ring; Rxp1 and Ryp1 each independently represent a group having a group selected from a (meth)acryloyl group, a styrene group, a vinyl group, an acetylene group, a maleimide group, an epoxy group, and an oxetane group; n represents an integer of 0 to 4; m represents an integer of 0 to 4; n+m represents an integer of 1 to 8; Rxp2 and Rxp3 each independently represent a hydrogen atom, an alkyl group, an aryl group, or a group represented by Rxp1.

[0162] The curable composition of the present invention preferably contains a resin as a dispersant. Examples of dispersants include acidic dispersants (acidic resins) and basic dispersants (basic resins). Here, the term "acidic dispersant (acidic resin)" refers to a resin in which the amount of acid groups is greater than the amount of basic groups. As the acidic dispersant (acidic resin), a resin in which the amount of acid groups is 70 mol% or more is preferred, assuming that the total amount of acid groups and basic groups is 100 mol%. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxy group. The acid value of the acidic dispersant (acidic resin) is preferably 10 to 105 mgKOH / g. Furthermore, the term "basic dispersant (basic resin)" refers to a resin in which the amount of basic groups is greater than the amount of acid groups. As the basic dispersant (basic resin), a resin in which the amount of basic groups is greater than 50 mol% is preferred, assuming that the total amount of acid groups and basic groups is 100 mol%. The basic group possessed by the basic dispersant is preferably an amino group.

[0163] The resin used as the dispersant is preferably a graft resin. For details of the graft resin, please refer to the description in paragraphs 0025 to 0094 of JP 2012-255128 A, the contents of which are incorporated herein by reference.

[0164] The resin used as the dispersant is preferably a resin having an aromatic carboxy group, such as those mentioned above.

[0165] The resin used as the dispersant is preferably a polyimine-based dispersant containing a nitrogen atom in at least one of the main chain and the side chain. The polyimine-based dispersant is preferably a resin having a main chain with a partial structure containing a functional group with a pKa of 14 or less and a side chain having 40 to 10,000 atoms, and having a basic nitrogen atom in at least one of the main chain and the side chain. There are no particular restrictions on the basic nitrogen atom, as long as it is a nitrogen atom that exhibits basicity. For details about polyimine-based dispersants, please refer to the description in paragraphs 0102 to 0166 of JP 2012-255128 A, the contents of which are incorporated herein by reference.

[0166] The resin used as a dispersant is preferably a resin having a structure in which multiple polymer chains are bonded to a core portion. Examples of such resins include dendrimers (including star-shaped polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.

[0167] The resin used as a dispersant is also preferably a resin containing a repeating unit having an ethylenically unsaturated bond-containing group in a side chain. The content of the repeating unit having an ethylenically unsaturated bond-containing group in a side chain is preferably 10 mol % or more, more preferably 10 to 80 mol %, and even more preferably 20 to 70 mol %, of all repeating units of the resin.

[0168] Examples of dispersants include resins described in JP 2018-087939 A, block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent No. 6432077 A, polyethyleneimine having a polyester side chain described in WO 2016 / 104803 A, block copolymers described in WO 2019 / 125940 A, block polymers having an acrylamide structural unit described in JP 2020-066687 A, block polymers having an acrylamide structural unit described in JP 2020-066688 A, dispersants described in WO 2016 / 104803 A, and those having a main chain described in WO 2021 / 182268 A ( Other examples that can be used include a resin having a graft structure in which the repeating unit is a (meth)acrylic repeating unit and the side chain has an oxetane group, a star polymer as described in WO 2021 / 187257, in which a part of the arm portion has a repeating unit having an oxetane group, a resin having an amic acid repeating unit in the main chain and a graft structure in the side chain as described in WO 2022 / 019253, a resin having an amic acid repeating unit in the main chain and a block polymer at the terminal as described in WO 2022 / 019254, and a resin having an amic acid repeating unit and a polyester repeating unit in the main chain and a graft structure in the side chain as described in WO 2022 / 019255.

[0169] Dispersants are also available as commercially available products, and specific examples thereof include the DISPERBYK series manufactured by BYK Chemie, the SOLSPERSE series manufactured by Lubrizol Japan, the Efka series manufactured by BASF, and the AJISPER series manufactured by Ajinomoto Fine-Techno Co., Ltd. In addition, the products described in paragraph 0129 of JP 2012-137564 A and the products described in paragraph 0235 of JP 2017-194662 A can also be used as dispersants.

[0170] The content of the resin in the total solid content of the curable composition is preferably 1 to 60% by mass. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less. The content of the resin having an acid group in the total solid content of the curable composition is preferably 1 to 60% by mass. The lower limit is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 15% by mass or more, and particularly preferably 20% by mass or more. The upper limit is preferably 50% by mass or less, and more preferably 40% by mass or less.

[0171] The content of the resin is preferably 100 to 1,000 parts by mass per 100 parts by mass of the polymerizable compound. The lower limit is preferably 150 parts by mass or more, and more preferably 200 parts by mass or more. The upper limit is preferably 600 parts by mass or less, and more preferably 500 parts by mass or less. The curable composition of the present invention may contain only one type of resin, or may contain two or more types. When two or more types of resins are contained, the total amount thereof preferably falls within the above range.

[0172] <<Colorant>> The curable composition of the present invention preferably contains a colorant. Examples of the colorant include a white colorant, a black colorant, a chromatic colorant, and an infrared-absorbing colorant. In the present invention, the white colorant includes not only pure white colorants but also light gray colorants close to white (for example, grayish white, light gray, etc.).

[0173] The coloring material may be a pigment or a dye. A pigment and a dye may be used in combination. The pigment may be either an inorganic pigment or an organic pigment, but is preferably an organic pigment from the viewpoints of a wide range of color variations, ease of dispersion, safety, etc. The coloring material preferably contains a pigment.

[0174] The average primary particle diameter of the pigment is preferably 1 to 200 nm. The lower limit is preferably 5 nm or more, more preferably 10 nm or more. The upper limit is preferably 180 nm or less, more preferably 150 nm or less, and even more preferably 100 nm or less. In this specification, the primary particle diameter of the pigment can be determined from a photograph obtained by observing the primary particles of the pigment with a transmission electron microscope. Specifically, the projected area of ​​the primary particles of the pigment is determined, and the corresponding circle-equivalent diameter is calculated as the primary particle diameter of the pigment.

[0175] The crystallite size of the pigment, determined from the half-width of a peak derived from any crystal plane in an X-ray diffraction spectrum obtained using CuKα radiation as an X-ray source, is preferably 0.1 to 100 nm, more preferably 0.5 to 50 nm, even more preferably 1 to 30 nm, and particularly preferably 5 to 25 nm.

[0176] The specific surface area of ​​the pigment is 1 to 300 m ２ / g. The lower limit is 10 m ２ / g or more, and ２ / g or more is more preferable. ２ / g or less, and ２ The value of the specific surface area can be determined according to the BET (Brunauer, Emmett and Teller) method in accordance with DIN 66131: Determination of the specific surface area of ​​solids by gas adsorption.

[0177] (Chromatic Colorant) Examples of chromatic colorants include colorants having a maximum absorption wavelength in the wavelength range of 400 to 700 nm, such as green colorants, red colorants, yellow colorants, purple colorants, blue colorants, and orange colorants.

[0178] Examples of the red colorant include a diketopyrrolopyrrole compound, an anthraquinone compound, an azo compound, a naphthol compound, an azomethine compound, a xanthene compound, a quinacridone compound, a perylene compound, and a thioindigo compound, and the like, preferably a diketopyrrolopyrrole compound, an anthraquinone compound, or an azo compound, and more preferably a diketopyrrolopyrrole compound. The red colorant is preferably a pigment (red pigment), and more preferably a diketopyrrolopyrrole pigment.

[0179] Specific examples of red colorants include C.I. (Color Index) Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2, 53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, Examples of red pigments include 150,155,166,168,169,170,171,172,175,176,177,178,179,184,185,187,188,190,200,202,206,207,208,209,210,216,220,224,226,242,246,254,255,264,269,270,272,279,291,294,295,296,297. In addition, as a red colorant, a compound described in paragraph number 0034 of WO 2022 / 085485, or a brominated diketopyrrolopyrrole compound described in JP-A-2020-085947 can also be used.

[0180] As the red colorant, C.I. Pigment Red 122, 177, 224, 254, 255, 264, 269, 272, and 291 are preferred, C.I. Pigment Red 254, 264, and 272 are more preferred, and C.I. Pigment Red 254 and 264 are even more preferred.

[0181] Examples of the green colorant include phthalocyanine compounds and squarylium compounds, and the phthalocyanine compounds are preferred. The green colorant is preferably a pigment (green pigment), and more preferably a phthalocyanine pigment.

[0182] Specific examples of green colorants include green pigments such as C.I. Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66. Furthermore, halogenated zinc phthalocyanine pigments having an average of 10 to 14 halogen atoms, an average of 8 to 12 bromine atoms, and an average of 2 to 5 chlorine atoms per molecule can also be used as green colorants. Specific examples include the compounds described in WO 2015 / 118720. Furthermore, compounds described in paragraph 0029 of WO 2022 / 085485, aluminum phthalocyanine compounds described in JP-A 2020-070426, and diarylmethane compounds described in JP-A 2020-504758 can also be used as green colorants.

[0183] As the green colorant, C.I. Pigment Green 7, 36, 58, 62, and 63 are preferred.

[0184] Examples of orange colorants include diketopyrrolopyrrole compounds and azo compounds. The orange colorant is preferably a pigment (orange pigment). Specific examples of orange colorants include orange pigments such as C.I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43, 46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, and 73.

[0185] Examples of the yellow colorant include an azo compound, an azomethine compound, an isoindoline compound, a pteridine compound, a quinophthalone compound, and a perylene compound. The yellow colorant is preferably a pigment (yellow pigment). Specific examples of the yellow colorant include C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125 , 126, 127, 128, 129, 137, 138, 139, 147, 148, 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, 193, 194, 199, 213, 214, 215, 228, 231, 232, 233, 234, 235, 236 and the like.

[0186] As the yellow coloring material, an azobarbituric acid nickel complex having the following structure can also be used.

[0187] As the yellow colorant, the compounds described in paragraphs 0031 to 0033 of WO 2022 / 085485, the methine dyes described in JP-A 2019-073695, and the methine dyes described in JP-A 2019-073696 can be used.

[0188] Examples of the purple colorant include an oxazine compound, a quinacridone compound, a perylene compound, and an indigo compound, and the oxazine compound is preferred. The purple colorant is preferably a pigment (purple pigment). Specific examples of the purple colorant include purple pigments such as C.I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

[0189] Examples of blue colorants include phthalocyanine compounds and squarylium compounds, with phthalocyanine compounds being preferred. The blue colorant is preferably a pigment (blue pigment). Specific examples of blue colorants include blue pigments such as C.I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 29, 60, 64, 66, 79, 80, 87, and 88. Furthermore, aluminum phthalocyanine compounds having phosphorus atoms can also be used as blue colorants. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A No. 2012-247591 and paragraph 0047 of JP-A No. 2011-157478.

[0190] Dyes can also be used as chromatic colorants. There are no particular limitations on the dyes, and known dyes can be used. Examples include pyrazole azo dyes, anilino azo dyes, triarylmethane dyes, anthraquinone dyes, anthrapyridone dyes, benzylidene dyes, oxonol dyes, pyrazolotriazole azo dyes, pyridone azo dyes, cyanine dyes, phenothiazine dyes, pyrrolopyrazole azomethine dyes, xanthene dyes, phthalocyanine dyes, benzopyran dyes, indigo dyes, and pyrromethene dyes.

[0191] A dye polymer can also be used as a chromatic colorant. The dye polymer is preferably a dye dissolved in a solvent when used. The dye polymer may also form particles. When the dye polymer is particulate, it is typically used in a dispersed state in a solvent. A particulate dye polymer can be obtained, for example, by emulsion polymerization, and specific examples of the compounds and production methods described in JP-A 2015-214682 include those described in JP-A 2015-214682. The dye polymer has two or more dye structures in one molecule, preferably three or more dye structures. The upper limit is not particularly limited, but can be 100 or less. The multiple dye structures in one molecule may be the same dye structure or different dye structures. The weight-average molecular weight (Mw) of the dye polymer is preferably 2,000 to 50,000. The lower limit is more preferably 3,000 or more, and even more preferably 6,000 or more. The upper limit is more preferably 30,000 or less, and even more preferably 20,000 or less. As the dye multimer, compounds described in JP-A-2011-213925, JP-A-2013-041097, JP-A-2015-028144, JP-A-2015-030742, WO 2016 / 031442, etc. can also be used.

[0192] As chromatic colorants, triarylmethane dye polymers described in Korean Patent Publication No. 10-2020-0028160, xanthene compounds described in JP 2020-117638 A, phthalocyanine compounds described in WO 2020 / 174991 A, isoindoline compounds described in JP 2020-160279 A or salts thereof, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069442 A, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069730 A, compounds represented by formula 1 described in Korean Patent Publication No. 10-2020-0069070 A Compounds represented by the formula 1 described in Korean Patent Publication No. 10-2020-0069067, compounds represented by the formula 1 described in Korean Patent Publication No. 10-2020-0069062, halogenated zinc phthalocyanine pigments described in Japanese Patent No. 6809649, isoindoline compounds described in JP-A-2020-180176, phenothiazine compounds described in JP-A-2021-187913, halogenated zinc phthalocyanines described in WO 2022 / 004261, and halogenated zinc phthalocyanines described in WO 2021 / 250883 can be used. The chromatic colorant may be a rotaxane, and the dye skeleton may be used in the cyclic structure of the rotaxane, in the rod-shaped structure, or in both structures. As chromatic colorants, quinophthalone compounds represented by formula 1 in Korean Patent Publication No. 10-2020-0030759, polymer dyes described in Korean Patent Publication No. 10-2020-0061793, chromatic colorants described in JP-A-2022-029701, isoindoline compounds described in WO 2022 / 014635, aluminum phthalocyanine compounds described in WO 2022 / 024926, and JP-A-2022-045 Compounds described in Patent Publication No. 895, compounds described in WO 2022 / 050051, compounds described in JP 2020-090676, compounds described in JP 2020-055956, compounds described in JP 2021-031681, compounds described in JP 2022-056354, compounds described in US Patent Application Publication No. 2021 / 0355327, compounds described in WO 2022 / 065357,Compounds described in JP 2020-045436 A, compounds described in Korean Patent Publication No. 10-2021-0146726 A, compounds described in JP 2018-178039 A, compounds described in Chinese Patent Publication No. 113881244 A, compounds described in Chinese Patent Publication No. 113881245 A, compounds described in Chinese Patent Publication No. 113881246 A, compounds described in JP 2022-1048 A compounds described in JP-A-2022-096701, compounds described in JP-A-2020-023652, green pigments described on pages 80 to 84 of the Journal of the Color Materials Association (published in 2022), compounds described in JP-A-2022-143135, compounds described in JP-A-2022-140287, compounds described in WO 2022 / 136308, Chinese Patent Application Publication No. 11306134 Perylene compounds described in Korean Patent Publication No. 10-2017-0018993, cyan pigments described in Korean Patent Publication No. 10-2017-0018993, isoindoline compounds described in Japanese Patent Application Laid-Open No. 2020-180176, compounds described in Japanese Patent Application Laid-Open No. 2023-013209, compounds described in Japanese Patent Application Laid-Open No. 2023-013166, xanthene compounds described in International Publication No. 2023 / 286526, compounds described in Japanese Patent Application Laid-Open No. 2021-155746 Compounds described in JP-A-2021-155747, compounds described in JP-A-2021-155748, compounds described in JP-A-2021-155749, compounds described in WO 2018 / 051876, compounds described in JP-A-2020-083981, compounds described in JP-A-2023-056463, compounds described in JP-T-2023-515473, and the like can also be used.

[0193] Two or more chromatic colorants may be used in combination. When two or more chromatic colorants are used in combination, the combination of the two or more chromatic colorants may form a black color. Examples of such combinations include the following embodiments (1) to (7). When the curable composition contains two or more chromatic colorants and exhibits a black color through the combination of the two or more chromatic colorants, the curable composition of the present invention can be preferably used as a curable composition for forming an infrared transmission filter. (1) An embodiment containing a red colorant and a blue colorant. (2) An embodiment containing a red colorant, a blue colorant, and a yellow colorant. (3) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a purple colorant. (4) An embodiment containing a red colorant, a blue colorant, a yellow colorant, a purple colorant, and a green colorant. (5) An embodiment containing a red colorant, a blue colorant, a yellow colorant, and a green colorant. (6) An embodiment containing a red colorant, a blue colorant, and a green colorant. (7) An embodiment containing a yellow coloring material and a purple coloring material.

[0194] (White coloring material) Examples of the white coloring material include inorganic pigments such as titanium oxide, strontium titanate, barium titanate, zinc oxide, magnesium oxide, zirconium oxide, aluminum oxide, barium sulfate, silica, talc, mica, aluminum hydroxide, calcium silicate, aluminum silicate, and zinc sulfide. As the white coloring material, the white pigments described in paragraphs 0040 to 0043 of WO 2022 / 085485 can be used.

[0195] (Black Colorant) The black colorant is not particularly limited, and known materials can be used. The black colorant may be an inorganic black colorant or an organic black colorant. The black colorant is preferably a pigment. In this specification, the black colorant refers to a colorant that exhibits absorption over the entire wavelength range of 400 to 700 nm.

[0196] Examples of inorganic black colorants include carbon black, titanium black, graphite, etc., with carbon black and titanium black being preferred, and titanium black being more preferred. Titanium black is a black particle containing titanium atoms, and low-order titanium oxide or titanium oxynitride is preferred. As the titanium black, the titanium black described in paragraph 0044 of WO 2022 / 085485 can be used. As the inorganic black colorant, zirconium nitride powder described in JP 2023-048173 A can also be used.

[0197] Examples of organic black colorants include bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds, with bisbenzofuranone compounds and perylene compounds being preferred. The organic black colorant may be a compound described in paragraph 0166 of International Publication No. 2022 / 065215. Furthermore, examples of organic black colorants include perylene black (such as Lumogen Black FK4280) described in paragraphs 0016 to 0020 of JP-A-2017-226821 and black azo pigments described in JP-A-2022-121935.

[0198] (Infrared absorbing colorant) The infrared absorbing colorant is preferably a compound having a maximum absorption wavelength longer than 700 nm. The infrared absorbing colorant is preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm to 1800 nm, more preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm to 1400 nm, even more preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm to 1200 nm, and particularly preferably a compound having a maximum absorption wavelength in the wavelength range of more than 700 nm to 1000 nm. In addition, the absorbance A of the infrared absorbing colorant at a wavelength of 500 nm is １ and absorbance A at the maximum absorption wavelength ２ Ratio A １ / A ２ is preferably 0.08 or less, more preferably 0.04 or less. The infrared absorbing colorant is preferably a pigment, more preferably an organic pigment.

[0199] Examples of infrared absorbing colorants include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, croconium compounds, oxonol compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiolene metal complexes, metal oxides, and metal borides. Specific examples of these include the compounds described in paragraph 0114 of WO 2022 / 065215. Examples of infrared absorbing colorants include the compounds described in paragraph 0121 of WO 2022 / 065215, squarylium compounds described in JP 2020-075959 A, Copper complexes described in Korean Patent Publication No. 10-2019-0135217, croconic acid compounds described in JP 2021-195515, infrared absorbing dyes described in JP 2022-022070, croconium compounds described in WO 2019 / 021767, compounds described in JP 2019-127549, compounds described in WO 2022 / 059619, and compounds described in JP 2022-151682 The compounds described in JP-A-2022-188858, the squarylium compounds described in JP-A-2022-184710, the compounds described in JP-A-2022-189736, the squarylium compounds described in JP-A-2023-004570, the squarylium compounds described in WO 2019 / 230660, and the compounds described in WO 2020 / 218615 can also be used.

[0200] The content of the colorant in the total solid content of the curable composition is preferably 30 to 80% by mass, with the upper limit being preferably 70% by mass or less, and more preferably 65% ​​by mass or less, and the lower limit being preferably 35% by mass or more, and more preferably 40% by mass or more.

[0201] The content of the pigment in the total solid content of the curable composition is preferably 20 to 80% by mass. The upper limit is preferably 75% by mass or less, more preferably 65% ​​by mass or less, and even more preferably 63% by mass or less. The lower limit is preferably 25% by mass or more, more preferably 30% by mass or more, and even more preferably 35% by mass or more. According to the curable composition of the present invention, even when the pigment content is high, it is possible to form a film in which foreign matter defects are suppressed, and therefore, when the pigment content is high, the effects of the present invention are more pronounced.

[0202] The content of the pigment in the coloring material is preferably 20 to 100% by mass, more preferably 50 to 100% by mass, and even more preferably 70 to 100% by mass.

[0203] <<Chain Transfer Agent>> The curable composition of the present invention preferably contains a chain transfer agent. According to this embodiment, it is possible to further increase the sensitivity when exposed to light having a wavelength of 150 to 300 nm, such as KrF radiation. Examples of the chain transfer agent include a thiol compound, a thiocarbonylthio compound, and a dimer of an aromatic α-methylalkenyl, and a thiol compound is preferred. Examples of the chain transfer agent include the compounds described in paragraphs 0093 to 0113 of WO 2019 / 188652.

[0204] The thiol compound used as a chain transfer agent is a compound having one or more thiol groups, preferably a compound having two or more thiol groups. The upper limit of the number of thiol groups contained in the thiol compound is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. The thiol compound is particularly preferably a compound having two thiol groups.

[0205] The thiol compound is preferably a compound represented by the following formula (SH-1): Ｓ１ - (SH) ｎ Formula (SH-1) (wherein SH represents a thiol group, L １ represents an n-valent group, where n is an integer of 1 or more.

[0206] L in formula (SH-1) Ｓ１ The n-valent group represented by is a hydrocarbon group, a heterocyclic group, —O—, —S—, —NR Ｓ１ -, -CO-, -COO-, -OCO-, -SO ２ - or a group consisting of a combination thereof. Ｓ１ represents a hydrogen atom, an alkyl group, or an aryl group, with a hydrogen atom being preferred. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group may be cyclic or acyclic. The aliphatic hydrocarbon group may be a saturated aliphatic hydrocarbon group or an unsaturated aliphatic hydrocarbon group. The hydrocarbon group may have a substituent or may not have a substituent. The cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be a monocyclic or fused ring. The heterocyclic group may be a monocyclic or fused ring. The heterocyclic group is preferably a 5- or 6-membered ring. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Examples of heteroatoms constituting the heterocyclic group include a nitrogen atom, an oxygen atom, and a sulfur atom. L １ The number of carbon atoms constituting the group is preferably 3 to 100, and more preferably 6 to 50.

[0207] In formula (SH-1), n ​​represents an integer of 1 or more. The upper limit of n is preferably 10 or less, more preferably 6 or less, and even more preferably 4 or less. The lower limit of n is preferably 2 or more.

[0208] Specific examples of thiol compounds include the compounds described in the Examples below and the compounds described in paragraphs 0100 to 0103 of WO 2019 / 188652. Commercially available thiol compounds include PEMP (manufactured by SC Organic Chemical Co., Ltd.), Suncera M (manufactured by Sanshin Chemical Industry Co., Ltd.), Karenz MTBD1, Karenz MTPE1, Karenz MTNR1, and Karenz MTTPMB (all manufactured by Resonac Corporation). The thiol compounds described in JP 2020-109068 A can also be used as chain transfer agents.

[0209] The molecular weight of the chain transfer agent is preferably 200 or more. The upper limit is preferably 1000 or less, more preferably 800 or less, and even more preferably 600 or less, because the SH valence per weight can be increased.

[0210] The content of the chain transfer agent in the total solid content of the curable composition is preferably 0.001 to 5% by mass. The upper limit is preferably 3% by mass or less, more preferably 1% by mass or less. The lower limit is preferably 0.05% by mass or more, more preferably 0.01% by mass or more. The content of the chain transfer agent is preferably 0.1 to 200 parts by mass per 100 parts by mass of the total of the specific oxime ester compound (E) and the specific oxime ester compound (Z). The upper limit is preferably 100 parts by mass or less, more preferably 50 parts by mass or less. The lower limit is preferably 0.5 parts by mass or more, more preferably 1 part by mass or more. Only one type of chain transfer agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

[0211] <<Amine Compound>> The curable compound of the present invention preferably contains an amine compound. By using the above-mentioned specific compound in combination with an amine compound, the biradical state of the specific compound undergoes radical transfer by hydrogen abstraction at the α-position of the amine, thereby further improving the efficiency of radical generation from the photopolymerization initiator during exposure and further accelerating the polymerization reaction of the polymerizable compound.

[0212] The molecular weight of the amine compound is preferably 100 to 1000. The upper limit is preferably 800 or less, more preferably 500 or less. The lower limit is preferably 150 or more, more preferably 200 or more.

[0213] The amine compound is preferably a compound having 1 to 8 amino groups in one molecule, more preferably a compound having 1 to 4 amino groups, and even more preferably a compound having 1 or 2 amino groups.

[0214] The amine compound is preferably colorless. That is, the molar absorption coefficient of the amine compound at wavelengths of 400 to 700 nm is 200 L mol －１ ・cm －１ It is preferable that the concentration is less than 100 L mol －１ ・cm －１ It is more preferable that it is less than 10 ...

[0215] The amine compound may be a primary, secondary or tertiary amine, but is preferably a tertiary amine.

[0216] In the amine compound, the three groups connected to the nitrogen atom are preferably selected from a hydrogen atom, an alkyl group, an aryl group, and a heteroaryl group, and a combination of an alkyl group and an aryl group is most preferred.

[0217] The amine compound preferably has any one of a carboxy group, a sulfonic acid group, a phosphoric acid group, and a hydroxy group, for the purpose of improving alkaline developability and reducing residues.

[0218] The amine compound is preferably a compound represented by formula (B-1). In formula (B-1), R ａ and R ｂ each independently represents a monovalent organic group having 1 to 10 carbon atoms which may contain a heteroatom; R ｃ represents a monovalent organic group which may contain a heteroatom; m represents an integer of 0 to 5;

[0219] R ａ , R ｂ and R ｃ Examples of the organic group represented by include an alkyl group, an aryl group, and a heteroaryl group, and an alkyl group is preferred. The alkyl group, the aryl group, and the heteroaryl group may have a substituent. Examples of the substituent include a carboxy group, a sulfonic acid group, a phosphate group, and a hydroxy group, and a hydroxy group is preferred. m represents an integer of 0 to 5, and is preferably an integer of 0 to 3, more preferably 0 or 1, and even more preferably 0.

[0220] Specific examples of the amine compound include compounds T-5 and T-6 described in the Examples below, Michler's ketone, 4,4'-bis(diethylamino)benzophenone, 2,5-bis(4'-diethylaminobenzal)cyclopentane, 2,6-bis(4'-diethylaminobenzal)cyclohexanone, 2,6-bis(4'-diethylaminobenzal)-4-methylcyclohexanone, 4,4'-bis(dimethylamino)chalcone, 4,4'-bis(diethylamino)chalcone, p -dimethylaminocinnamylidene indanone, p-dimethylaminobenzylidene indanone, 2-(p-dimethylaminophenylbiphenylene)-benzothiazole, 2-(p-dimethylaminophenylvinylene)benzothiazole, 2-(p-dimethylaminophenylvinylene)isonaphthothiazole, 1,3-bis(4'-dimethylaminobenzal)acetone, 1,3-bis(4'-diethylaminobenzal)acetone, 3,3'-carbonyl-bis(7-diethylaminobenzal)acetone coumarin), 3-acetyl-7-dimethylaminocoumarin, 3-ethoxycarbonyl-7-dimethylaminocoumarin, 3-benzyloxycarbonyl-7-dimethylaminocoumarin, 3-methoxycarbonyl-7-diethylaminocoumarin, 3-ethoxycarbonyl-7-diethylaminocoumarin, N-phenyl-N'-ethylethanolamine, N-phenyldiethanolamine, N-p-tolyldiethanolamine, N-phenylethanolamine, 4-morpholino Examples thereof include benzophenone, isoamyl dimethylaminobenzoate, isoamyl diethylaminobenzoate, 2-mercaptobenzimidazole, 1-phenyl-5-mercaptotetrazole, 2-mercaptobenzothiazole, 2-(p-dimethylaminostyryl)benzoxazole, 2-(p-dimethylaminostyryl)benzthiazole, 2-(p-dimethylaminostyryl)naphtho(1,2-d)thiazole, and 2-(p-dimethylaminobenzoyl)styrene. These may be used alone or in combination of, for example, 2 to 5 types.

[0221] The content of the amine compound is preferably 5 to 1,000 parts by mass relative to 100 parts by mass of the specific compound. The upper limit is preferably 500 parts by mass or less, more preferably 200 parts by mass or less. The lower limit is preferably 10 parts by mass or more, more preferably 20 parts by mass or more.

[0222] <<Pigment Derivative>> The curable composition of the present invention may contain a pigment derivative. The pigment derivative is used, for example, as a dispersing aid. A dispersing aid is a material that enhances the dispersibility of a colorant such as a pigment in the curable composition.

[0223] Examples of the pigment derivative include a compound having at least one structure selected from the group consisting of a dye structure and a triazine structure, and an acid group or a basic group.

[0224] Examples of the dye structure include a quinoline dye structure, a benzimidazolone dye structure, a benzisoindole dye structure, a benzothiazole dye structure, an iminium dye structure, a squarylium dye structure, a croconium dye structure, an oxonol dye structure, a pyrrolopyrrole dye structure, a diketopyrrolopyrrole dye structure, an azo dye structure, an azomethine dye structure, a phthalocyanine dye structure, a naphthalocyanine dye structure, an anthraquinone dye structure, a quinacridone dye structure, a dioxazine dye structure, a perinone dye structure, a perylene dye structure, a thiazineindigo dye structure, a thioindigo dye structure, an isoindoline dye structure, an isoindolinone dye structure, a quinophthalone dye structure, a dithiol dye structure, a triarylmethane dye structure, and a pyrromethene dye structure.

[0225] Examples of the acid group possessed by the pigment derivative include a carboxy group, a sulfo group, a phosphate group, a boronic acid group, an imidic acid group, and salts thereof. Examples of the atom or atomic group constituting the salt include an alkali metal ion (Li ＋ , Na ＋ , K. ＋ etc.), alkaline earth metal ions (Ca ２＋ , Mg ２＋Examples of the imide acid group include an ammonium ion, an imidazolium ion, a pyridinium ion, and a phosphonium ion. ２ NHSO ２ R Ｘ１ , -CONHSO ２ R Ｘ２ , -CONHCOR Ｘ３ or -SO ２ NHCOR Ｘ４ A group represented by the formula: ２ NHSO ２ R Ｘ１ , -CONHSO ２ R Ｘ２ , or -SO ２ NHCOR Ｘ４ A group represented by the formula: ２ NHSO ２ R Ｘ１ or -CONHSO ２ R Ｘ２ is more preferred. Ｘ１ ~R Ｘ４ R each independently represents an alkyl group or an aryl group. Ｘ１ ~R Ｘ４ The alkyl group and aryl group represented by R may have a substituent. The substituent is preferably a halogen atom, more preferably a fluorine atom. Ｘ１ ~R Ｘ４ are each independently preferably an alkyl group containing a fluorine atom or an aryl group containing a fluorine atom, and more preferably an alkyl group containing a fluorine atom. The number of carbon atoms in the alkyl group containing a fluorine atom is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. The number of carbon atoms in the aryl group containing a fluorine atom is preferably 6 to 20, more preferably 6 to 12, and even more preferably 6.

[0226] Examples of basic groups possessed by the pigment derivative include amino groups, pyridinyl groups and their salts, ammonium salts, and phthalimidomethyl groups. Examples of atoms or atomic groups that constitute the salts include hydroxide ions, halogen ions, carboxylate ions, sulfonate ions, and phenoxide ions.

[0227] The amino group is —NR ｘ１１ R ｘ１２ and a cyclic amino group.

[0228] -NR ｘ１１ R ｘ１２ In the group represented by ｘ１１ and R ｘ１２ are each independently a hydrogen atom, an alkyl group, or an aryl group, and are preferably an alkyl group. That is, the amino group is preferably a dialkylamino group. The alkyl group preferably has 1 to 10 carbon atoms, more preferably 1 to 5, and even more preferably 1 to 3. The alkyl group may be linear, branched, or cyclic, but is preferably linear or branched, and more preferably linear. The alkyl group may have a substituent. The aryl group preferably has 6 to 30 carbon atoms, more preferably 6 to 20, and even more preferably 6 to 12. The aryl group may have a substituent.

[0229] Examples of the cyclic amino group include a pyrrolidine group, a piperidine group, a piperazine group, a morpholine group, etc. These groups may further have a substituent.

[0230] The pigment derivative may be a pigment derivative having excellent visible transparency (hereinafter also referred to as a transparent pigment derivative). The maximum molar absorption coefficient (εmax) of the transparent pigment derivative in the wavelength range of 400 to 700 nm is 3000 L mol －１ ・cm －１ It is preferable that the concentration is 1000 L mol or less. －１ ・cm －１ More preferably, it is 100 L mol or less. －１ ・cm －１ The lower limit of εmax is, for example, 1 L mol －１ ・cm －１ or more, and 10 L mol －１ ・cm －１ More than that is fine.

[0231] Specific examples of pigment derivatives include the compounds described in the examples below, the compounds described in paragraph 0124 of WO 2022 / 085485, the benzimidazolone compounds or salts thereof described in JP 2018-168244 A, compounds having an isoindoline skeleton described in general formula (1) of Japanese Patent No. 6996282, compounds described in JP 2019-172968 A, and compounds described in the specification of Chinese Patent Application Publication No. 115124889.

[0232] The content of the pigment derivative is preferably 1 to 30 parts by mass, and more preferably 3 to 20 parts by mass, relative to 100 parts by mass of the pigment. The total content of the pigment derivative and colorant is preferably 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more, based on the total solid content of the curable composition. The upper limit is preferably 80% by mass or less, and more preferably 70% by mass or less. Only one type of pigment derivative may be used, or two or more types may be used in combination.

[0233] <<Polyalkyleneimine>> The curable composition of the present invention can also contain a polyalkyleneimine. The polyalkyleneimine is used, for example, as a dispersing aid for pigments. A dispersing aid is a material for improving the dispersibility of coloring materials such as pigments in a curable composition. The polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine. The polyalkyleneimine is preferably a polymer having a branched structure containing a primary amino group, a secondary amino group, and a tertiary amino group. The alkyleneimine preferably has 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms, even more preferably 2 or 3 carbon atoms, and particularly preferably 2 carbon atoms.

[0234] The molecular weight of the polyalkyleneimine is preferably 200 or more, more preferably 250 or more. The upper limit is preferably 100,000 or less, more preferably 50,000 or less, even more preferably 10,000 or less, and particularly preferably 2,000 or less. Regarding the molecular weight value of the polyalkyleneimine, if the molecular weight can be calculated from the structural formula, the molecular weight of the polyalkyleneimine is the value calculated from the structural formula. On the other hand, if the molecular weight of the specific amine compound cannot be calculated from the structural formula or calculation is difficult, the number average molecular weight value measured by the boiling point elevation method is used. If the number average molecular weight cannot be measured by the boiling point elevation method or is difficult to measure, the number average molecular weight value measured by the viscosity method is used. If the number average molecular weight cannot be measured by the viscosity method or is difficult to measure, the number average molecular weight value measured in terms of polystyrene by GPC (gel permeation chromatography) is used.

[0235] The amine value of the polyalkyleneimine is preferably 5 mmol / g or more, more preferably 10 mmol / g or more, and even more preferably 15 mmol / g or more.

[0236] Specific examples of alkyleneimines include ethyleneimine, propyleneimine, 1,2-butyleneimine, and 2,3-butyleneimine, with ethyleneimine or propyleneimine being preferred, and ethyleneimine being more preferred. It is particularly preferred that the polyalkyleneimine be polyethyleneimine. Furthermore, the polyethyleneimine preferably contains primary amino groups in an amount of 10 mol% or more, more preferably 20 mol% or more, and even more preferably 30 mol% or more, based on the total of primary amino groups, secondary amino groups, and tertiary amino groups. Commercially available polyethyleneimines include Epomin SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by Nippon Shokubai Co., Ltd.).

[0237] The content of the polyalkyleneimine in the total solid content of the curable composition is preferably 0.1 to 5% by mass. The lower limit is preferably 0.2% by mass or more, more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is preferably 4.5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less. The content of the polyalkyleneimine is preferably 0.5 to 20 parts by mass per 100 parts by mass of the pigment. The lower limit is preferably 0.6 parts by mass or more, more preferably 1 part by mass or more, and even more preferably 2 parts by mass or more. The upper limit is preferably 10 parts by mass or less, and even more preferably 8 parts by mass or less. Only one type of polyalkyleneimine may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof is within the above range.

[0238] <<Solvent>> The curable composition of the present invention preferably contains a solvent. Examples of the solvent include organic solvents. The type of solvent is basically not particularly limited as long as the solubility of each component and the coatability of the composition are satisfied. Examples of organic solvents include ester-based solvents, ketone-based solvents, alcohol-based solvents, amide-based solvents, ether-based solvents, and hydrocarbon-based solvents. For details of these, please refer to paragraph 0223 of WO 2015 / 166779, the contents of which are incorporated herein by reference. Furthermore, ester-based solvents substituted with a cyclic alkyl group and ketone-based solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of organic solvents include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl cellosolve acetate, ethyl lactate, diethylene glycol dimethyl ether, butyl acetate, methyl 3-methoxypropionate, 2-heptanone, 2-pentanone, 3-pentanone, 4-heptanone, cyclohexanone, 2-methylcyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, cycloheptanone, cyclooctanone, cyclohexyl acetate, cyclopentanone, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether ... Examples of suitable ethylene glycol monomethyl ether acetate include 3-methoxy-N,N-dimethylpropanamide, 3-butoxy-N,N-dimethylpropanamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, gamma butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, butane-1,3-diyl diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as diacetone alcohol, 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, and isopropyl alcohol.However, it may be preferable to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) used as organic solvents for environmental reasons (for example, the amount may be 50 ppm by mass (parts per million) or less, 10 ppm by mass or less, or 1 ppm by mass or less, relative to the total amount of organic solvents).

[0239] The metal content of the organic solvent is preferably low. The metal content of the organic solvent is preferably, for example, 10 parts per billion (ppb) by mass or less. If necessary, an organic solvent having a metal content of ppt (parts per trillion) by mass may be used, and such an organic solvent is provided, for example, by Toyo Gosei Co., Ltd. (The Chemical Daily, November 13, 2015).

[0240] Methods for removing impurities such as metals from organic solvents include, for example, distillation (molecular distillation, thin-film distillation, etc.) and filtration using a filter. The pore size of the filter used for filtration is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The filter material is preferably polytetrafluoroethylene, polyethylene, or nylon.

[0241] The organic solvent may contain isomers (compounds having the same number of atoms but different structures). The organic solvent may contain only one type of isomer or multiple types of isomers.

[0242] The organic solvent preferably has a peroxide content of 0.8 mmol / L or less, and more preferably contains substantially no peroxide.

[0243] The content of the solvent in the curable composition is preferably from 10 to 95% by mass, more preferably from 20 to 90% by mass, and even more preferably from 30 to 90% by mass.

[0244] From the viewpoint of environmental regulations, it is preferable that the curable composition of the present invention is substantially free of environmentally restricted substances. In the present invention, "substantially free of environmentally restricted substances" means that the content of environmentally restricted substances in the curable composition is 50 ppm by mass or less, preferably 30 ppm by mass or less, more preferably 10 ppm by mass or less, and particularly preferably 1 ppm by mass or less. Examples of environmentally restricted substances include benzene; alkylbenzenes such as toluene and xylene; and halogenated benzenes such as chlorobenzene. These substances are registered as environmentally restricted substances under the REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulations, the PRTR (Pollutant Release and Transfer Register) Act, the VOC (Volatile Organic Compounds) regulations, etc., and their usage amounts and handling methods are strictly regulated. These compounds may be used as solvents when producing the components used in the curable composition, and may be mixed into the curable composition as residual solvents. From the viewpoints of human safety and environmental considerations, it is preferable to reduce these substances as much as possible. Examples of methods for reducing environmentally restricted substances include a method in which the system is heated or depressurized to a temperature above the boiling point of the environmentally restricted substance, thereby distilling off the environmentally restricted substance from the system. Furthermore, when distilling off a small amount of environmentally regulated substances, it is useful to perform azeotropy with a solvent having a boiling point equivalent to that of the solvent in question in order to increase efficiency. Furthermore, when a radically polymerizable compound is contained, a polymerization inhibitor or the like may be added prior to distillation under reduced pressure to prevent intermolecular crosslinking due to the progress of a radical polymerization reaction during distillation under reduced pressure. These distillation methods can be used at any stage, such as the stage of raw materials, the stage of a product obtained by reacting the raw materials (e.g., a resin solution or a polyfunctional monomer solution after polymerization), or the stage of a curable composition prepared by mixing these compounds.

[0245] <<Compound Having a Cyclic Ether Group>> The curable composition of the present invention can contain a compound having a cyclic ether group. Examples of the cyclic ether group include an epoxy group and an oxetanyl group. The epoxy group may be an alicyclic epoxy group. The alicyclic epoxy group refers to a monovalent functional group having a cyclic structure in which an epoxy ring and a saturated hydrocarbon ring are condensed. The compound having a cyclic ether group is preferably a compound having an epoxy group (hereinafter also referred to as an epoxy compound). Examples of epoxy compounds include compounds having one or more epoxy groups per molecule, and compounds having two or more epoxy groups are preferred. The epoxy compound is preferably a compound having 1 to 100 epoxy groups per molecule. The upper limit of the number of epoxy groups contained in the epoxy compound can be, for example, 10 or less, or 5 or less. The lower limit of the number of epoxy groups contained in the epoxy compound is preferably 2 or more.

[0246] Examples of compounds having a cyclic ether group include the compounds described in paragraphs 0034 to 0036 of JP-A-2013-011869, 0147 to 0156 of JP-A-2014-043556, and 0085 to 0092 of JP-A-2014-089408, and the compounds described in JP-A-2017-179172, the xanthene epoxy resins described in JP-A-2021-195421, and the xanthene epoxy resins described in JP-A-2021-195422 can be used.

[0247] The compound having a cyclic ether group may be a low molecular weight compound (for example, a molecular weight of less than 2000, or even less than 1000) or a high molecular weight compound (macromolecule) (for example, a molecular weight of 1000 or more, and in the case of a polymer, a weight average molecular weight of 1000 or more). The weight average molecular weight of the compound having a cyclic ether group is preferably 200 to 100,000, and more preferably 500 to 50,000. The upper limit of the weight average molecular weight is preferably 10,000 or less, more preferably 5,000 or less, and even more preferably 3,000 or less.

[0248] Commercially available examples of compounds having a cyclic ether group include EHPE3150 (manufactured by Daicel Corporation), EPICLON N-695 (manufactured by DIC Corporation), Marproof G-0150M, G-0105SA, G-0130SP, G-0250SP, G-1005S, G-1005SA, G-1010S, G-2050M, G-01100, and G-01758 (all manufactured by NOF Corporation, epoxy group-containing polymers).

[0249] The content of the compound having a cyclic ether group in the total solid content of the curable composition is preferably 0.1 to 20% by mass. The lower limit is preferably 0.5% by mass or more, and more preferably 1% by mass or more. The upper limit is preferably 15% by mass or less, and more preferably 10% by mass or less. Only one type of compound having a cyclic ether group may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount thereof be in the above range.

[0250] <<UV Absorber>> The curable composition of the present invention may contain an UV absorber. Examples of UV absorbers include conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, and dibenzoyl compounds. Specific examples of such compounds include the compound described in paragraph 0179 of WO 2022 / 085485, the reactive triazine UV absorber described in JP 2021-178918 A, the UV absorber described in JP 2022-007884 A, the compound described in Korean Patent Publication No. 10-2022-0014454, and the compound described in JP 2023-013321 A can also be used. The content of the UV absorber in the total solids content of the curable composition is preferably 0.01 to 10% by mass, more preferably 0.01 to 5% by mass. The ultraviolet absorber may be used alone or in combination of two or more kinds. When two or more kinds are used, the total amount thereof is preferably in the above range.

[0251] <<Polymerization Inhibitor>> The curable composition of the present invention may contain a polymerization inhibitor. Examples of polymerization inhibitors include hydroquinone, p-methoxyphenol, di-tert-butyl-p-cresol, pyrogallol, tert-butylcatechol, benzoquinone, 4,4'-thiobis(3-methyl-6-tert-butylphenol), 2,2'-methylenebis(4-methyl-6-t-butylphenol), and N-nitrosophenylhydroxyamine salts (ammonium salts, cerous salts, etc.). Of these, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the curable composition is preferably 0.0001 to 5 mass%. One type of polymerization inhibitor may be used alone, or two or more types may be used. When two or more types are used, the total amount is preferably within the above range.

[0252] <<Silane Coupling Agent>> The curable composition of the present invention may contain a silane coupling agent. Examples of the silane coupling agent include silane compounds having a hydrolyzable group, and preferably silane compounds having a hydrolyzable group and other functional groups. The hydrolyzable group refers to a substituent directly bonded to a silicon atom that can form 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, and an acyloxy group, with an alkoxy group being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group. Examples of functional groups other than the hydrolyzable group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, a mercapto group, an epoxy group, an oxetanyl group, an amino group, a ureido group, a sulfide group, an isocyanate group, and a phenyl group, with an amino group, a (meth)acryloyl group, and an epoxy group being preferred. Specific examples of the silane coupling agent include the compound described in paragraph 0177 of WO 2022 / 085485 and the compound described in JP 2019-183020 A. The content of the silane coupling agent in the total solid content of the curable composition is preferably 0.1 to 15% by mass. The upper limit is preferably 10% by mass or less, more preferably 5% by mass or less. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more. Only one type of silane coupling agent may be used, or two or more types may be used. When two or more types are used, it is preferable that the total amount is within the above range.

[0253] <<Surfactant>> The curable composition of the present invention may contain a surfactant. As the surfactant, various surfactants such as a fluorine-based surfactant, a nonionic surfactant, a cationic surfactant, an anionic surfactant, and a silicone-based surfactant may be used. The surfactant is preferably a silicone-based surfactant or a fluorine-based surfactant, and more preferably a silicone-based surfactant. For details of the surfactant, reference may be made to the surfactants described in paragraphs 0238 to 0245 of WO 2015 / 166779, the contents of which are incorporated herein by reference.

[0254] As the fluorine-based surfactant, compounds described in paragraphs 0167 to 0173 of WO 2022 / 085485 can be used.

[0255] Examples of nonionic surfactants include the compounds described in paragraph 0174 of WO 2022 / 085485.

[0256] Silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419. OIL (all manufactured by Dow Toray Industries, Inc.), TSF-4300, TSF-4445, TSF-4460, TSF-4452 (all manufactured by Momentive Performance Materials), KP-341, KF-6000, KF-6001, KF-6002, KF-6003 (all manufactured by Shin-Etsu Chemical Co., Ltd.), BYK-307, BYK-322, BYK-323, BYK-330, BYK-333, BYK-3760, BYK-UV3510 (all manufactured by BYK-Chemie). Furthermore, compounds having the following structure can also be used as the silicone surfactant.

[0257] The content of the surfactant in the total solid content of the curable composition is preferably 0.001% by mass to 5.0% by mass, more preferably 0.005% by mass to 3.0% by mass. The surfactant may be one type or two or more types. When two or more types are used, it is preferable that the total amount is in the above range.

[0258] <<Antioxidant>> The curable composition of the present invention may contain an antioxidant. Examples of the antioxidant include phenolic antioxidants, amine antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants. Examples of the phenolic antioxidant include hindered phenol compounds. The phenolic antioxidant is preferably a compound having a substituent at the position adjacent to the phenolic hydroxy group (ortho position). The substituent is preferably a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms. The antioxidant is also preferably a compound having a phenol group and a phosphite ester group in the same molecule. Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, ethyl bis(2,4-di-tert-butyl-6-methylphenyl)phosphite, and tris(2,4-di-tert-butylphenyl)phosphite. Commercially available antioxidants include, for example, ADK STAB AO-20, ADK STAB AO-30, ADK STAB AO-40, ADK STAB AO-50, ADK STAB AO-50F, ADK STAB AO-60, ADK STAB AO-60G, ADK STAB AO-80, ADK STAB AO-330 (manufactured by ADEKA Corporation), and JP-650 (manufactured by Johoku Chemical Industry Co., Ltd.). Antioxidants include the compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, the compounds described in WO 2017 / 006600, the compounds described in WO 2017 / 164024, and the compounds described in Korean Patent Publication No. 10-2019-0059371. The content of the antioxidant in the total solid content of the curable composition is preferably 0.01 to 20 mass %, more preferably 0.3 to 15 mass %. Only one type of antioxidant may be used, or two or more types may be used. When two or more types are used, the total amount thereof is preferably within the above range.

[0259] <<Other Components>> The curable composition of the present invention may contain, as necessary, a sensitizer, a plasticizer, and other auxiliaries (e.g., conductive particles, fillers, antifoaming agents, flame retardants, leveling agents, release promoters, fragrances, surface tension modifiers, chain transfer agents, etc.). By appropriately incorporating these components, properties such as film properties can be adjusted. As these components, the compounds described in paragraph 0182 of WO 2022 / 085485 can be used.

[0260] The curable composition of the present invention may contain a metal oxide in order to adjust the refractive index of the resulting film. Examples of the metal oxide include TiO ２ , ZrO ２ , Al ２ O ３ , SiO ２ The primary particle size of the metal oxide is preferably 1 to 100 nm, more preferably 3 to 70 nm, and even more preferably 5 to 50 nm. The metal oxide may have a core-shell structure. In this case, the core may be hollow.

[0261] The curable composition of the present invention may contain a light resistance improver. Examples of the light resistance improver include the compounds described in paragraph 0183 of WO 2022 / 085485.

[0262] It is also preferable that the curable composition of the present invention is substantially free of terephthalic acid esters. Here, "substantially free" means that the content of terephthalic acid esters in the total amount of the curable composition is 1,000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero.

[0263] In view of environmental regulations, the curable composition of the present invention preferably has a melamine content of 10,000 ppm by mass or less.

[0264] The curable composition of the present invention preferably has a free metal content of 100 ppm or less, more preferably 50 ppm or less. The free halogen content is preferably 100 ppm or less, more preferably 50 ppm or less. Methods for reducing the free metals and halogens in the curable composition include washing with ion-exchanged water, filtration, ultrafiltration, and purification with an ion-exchange resin.

[0265] From the standpoint of environmental regulations, the use of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts may be restricted. When the content of the above-mentioned compounds in the curable composition of the present invention is reduced, the content of perfluoroalkyl sulfonic acids (particularly perfluoroalkyl sulfonic acids having a perfluoroalkyl group of 6 to 8 carbon atoms) and their salts, and perfluoroalkyl carboxylic acids (particularly perfluoroalkyl carboxylic acids having a perfluoroalkyl group of 6 to 8 carbon atoms) and their salts is preferably in the range of 0.01 ppb to 1000 ppb, more preferably in the range of 0.05 ppb to 500 ppb, and even more preferably in the range of 0.1 ppb to 300 ppb, relative to the total solids content of the curable composition. The curable composition of the present invention may be substantially free of perfluoroalkyl sulfonic acids and their salts, and perfluoroalkyl carboxylic acids and their salts. For example, by using a compound that can replace perfluoroalkyl sulfonic acid and its salt, and a compound that can replace perfluoroalkyl carboxylic acid and its salt, a curable composition that is substantially free of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt may be selected. Examples of compounds that can replace restricted compounds include compounds that are exempt from restrictions due to differences in the number of carbon atoms in the perfluoroalkyl group. However, the above does not preclude the use of perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt. The curable composition of the present invention may contain perfluoroalkyl sulfonic acid and its salt, and perfluoroalkyl carboxylic acid and its salt, within the maximum allowable range.

[0266] The water content of the curable composition of the present invention is usually 3% by mass or less, preferably 0.01 to 1.5% by mass, and more preferably 0.1 to 1.0% by mass. The water content can be measured by the Karl Fischer method.

[0267] The curable composition of the present invention can be used by adjusting the viscosity for the purpose of adjusting the film surface state (flatness, etc.), adjusting the film thickness, etc. The viscosity value can be appropriately selected as needed, but is preferably 0.3 mPa·s to 50 mPa·s, and more preferably 0.5 mPa·s to 20 mPa·s at 25°C. The viscosity can be measured, for example, using a cone-plate type viscometer with the temperature adjusted to 25°C.

[0268] <<Storage Container>> The container for storing the curable composition is not particularly limited, and any known container can be used. In addition, the container described in paragraph 0187 of WO 2022 / 085485 can be used as the storage container.

[0269] <Method for preparing curable composition> The curable composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the curable composition, all components may be simultaneously dissolved and / or dispersed in a solvent to prepare the curable composition, or, if necessary, each component may be prepared as two or more appropriate solutions or dispersions, which are mixed at the time of use (application) to prepare the curable composition.

[0270] The preparation of the curable composition preferably includes a process for dispersing the pigment. In the process for dispersing the pigment, mechanical forces used to disperse the pigment include compression, squeezing, impact, shear, and cavitation. Specific examples of these processes include a bead mill, a sand mill, a roll mill, a ball mill, a paint shaker, a microfluidizer, a high-speed impeller, a sand grinder, a flow jet mixer, high-pressure wet atomization, and ultrasonic dispersion. Furthermore, when grinding the pigment in a sand mill (bead mill), it is preferable to use small-diameter beads, increase the bead packing ratio, or otherwise increase the grinding efficiency under such conditions. Furthermore, it is preferable to remove coarse particles after the grinding process by filtration, centrifugation, or the like. In addition, the process and disperser for dispersing pigments can be suitably used, for example, the process and disperser described in "Dispersion Technology Encyclopedia," published by Joho Kiko Co., Ltd., July 15, 2005, or "Dispersion Technology and Industrial Applications Focused on Suspension (Solid / Liquid Dispersion System) - Comprehensive Data Collection," published by the Management Development Center Publishing Department, October 10, 1978, and paragraph 0022 of JP 2015-157893 A. In addition, in the process for dispersing pigments, particle refinement may be performed in a salt milling process. For details on the materials, equipment, processing conditions, etc. used in the salt milling process, see, for example, JP 2015-194521 A and JP 2012-046629 A. Examples of materials for beads used in dispersion include zirconia, agate, quartz, titania, tungsten carbide, silicon nitride, alumina, stainless steel, and glass. The beads may also be made of an inorganic compound having a Mohs hardness of at least 2. The curable composition may contain 1 to 10,000 ppm of the beads.

[0271] When preparing the curable composition, it is preferable to filter the curable composition with a filter for the purpose of removing foreign matter, reducing defects, etc. Examples of the type of filter and filtration method used for filtration include the filters and filtration methods described in paragraphs 0196 to 0199 of WO 2022 / 085485.

[0272] <Film> The film of the present invention is obtained from the curable composition of the present invention described above. The film of the present invention can be used for optical filters such as color filters, infrared transmission filters, and infrared cut filters.

[0273] The thickness of the film of the present invention can be adjusted appropriately depending on the purpose. For example, the thickness is preferably 20 μm or less, more preferably 10 μm or less, and even more preferably 5 μm or less. The lower limit of the thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0274] When the film of the present invention is used as a color filter, the film of the present invention preferably has a green, red, blue, cyan, magenta, or yellow hue. The film of the present invention can also be preferably used as a color pixel of a color filter. Examples of the color pixel include a red pixel, a green pixel, a blue pixel, a magenta pixel, a cyan pixel, and a yellow pixel, with a red pixel being more preferred.

[0275] <Pixel Manufacturing Method> A pixel manufacturing method using the curable composition of the present invention will be described. The pixel manufacturing method includes the steps of forming a curable composition layer on a support using the curable composition of the present invention, exposing the curable composition layer to light having a wavelength of 150 to 300 nm to form a pattern, and developing and removing the unexposed areas of the curable composition layer. Optionally, a step of baking the curable composition layer (pre-baking step) and a step of baking the developed pattern (pixel) (post-baking step) may be provided.

[0276] In the step of forming a curable composition layer, the curable composition layer is formed on a support using the curable composition of the present invention. The support is not particularly limited and can be appropriately selected depending on the application. Examples include a glass substrate and a silicon substrate, with a silicon substrate being preferred. The silicon substrate may also be formed with a charge-coupled device (CCD), a complementary metal-oxide semiconductor (CMOS), a transparent conductive film, or the like. A black matrix is ​​sometimes formed on the silicon substrate to isolate each pixel. The silicon substrate may also be provided with an underlayer to improve adhesion with an upper layer, prevent diffusion of substances, or flatten the substrate surface. The surface contact angle of the underlayer is preferably 20 to 70° when measured with diiodomethane. It is also preferably 30 to 80° when measured with water.

[0277] Known methods can be used as the coating method for the curable composition. For example, a dropping method (drop casting); a slit coating method; a spray method; a roll coating method; a rotary coating method (spin coating); a casting coating method; a slit and spin method; a pre-wetting method (for example, the method described in JP 2009-145395 A); inkjet (for example, on-demand method, piezo method, thermal method), various printing methods such as nozzle jet and other ejection printing, flexographic printing, screen printing, gravure printing, reverse offset printing, metal mask printing; a transfer method using a mold or the like; a nanoimprint method, etc. can also be mentioned. In addition, the coating method described in paragraph 0207 of WO 2022 / 085485 A can also be used.

[0278] The curable composition layer formed on the support may be dried (prebaked). When a film is produced by a low-temperature process, prebaking may not be performed. When prebaking is performed, the prebaking temperature is preferably 150°C or lower, more preferably 120°C or lower, and even more preferably 110°C or lower. The lower limit can be, for example, 50°C or higher, or can also be 80°C or higher. The prebaking time is preferably 10 to 300 seconds, more preferably 40 to 250 seconds, and even more preferably 80 to 220 seconds. Prebaking can be performed using a hot plate, an oven, or the like.

[0279] Next, the curable composition layer is irradiated with light having a wavelength of 150 to 300 nm to be patternwise exposed (exposure step). For example, the curable composition layer can be patternwise exposed by exposing it through a mask having a predetermined mask pattern using a stepper exposure machine, a scanner exposure machine, or the like. This allows the exposed portions to be cured.

[0280] Examples of light having a wavelength of 150 to 300 nm used for exposure include KrF radiation (wavelength 248 nm) and ArF radiation (wavelength 193 nm), with KrF radiation (wavelength 248 nm) being preferred. The light having a wavelength of 150 to 300 nm is preferably excimer laser light having a wavelength of 150 to 300 nm.

[0281] The exposure may be performed by continuous irradiation with light or by pulsed irradiation (pulse exposure), which is an exposure method in which light is repeatedly irradiated and paused in a short cycle (for example, on the order of milliseconds or less).

[0282] The irradiation amount (exposure amount) is, for example, 0.03 to 2.5 J / cm ２ is preferred, and 0.05 to 1.0 J / cm ２ The oxygen concentration during exposure can be appropriately selected. In addition to being performed in the atmosphere, exposure may be performed in a low-oxygen atmosphere with an oxygen concentration of 19% by volume or less (e.g., 15% by volume, 5% by volume, or substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration of more than 21% by volume (e.g., 22% by volume, 30% by volume, or 50% by volume). The exposure illuminance can be appropriately set, and is usually 1000 W / m ２ ~100000W / m ２ (For example, 5000 W / m ２ , 15000W / m ２ , or 35,000 W / m ２ The oxygen concentration and exposure illuminance may be appropriately combined. For example, an oxygen concentration of 10% by volume and an illuminance of 10,000 W / m ２ , oxygen concentration 35% by volume, illuminance 20,000 W / m ２ etc.

[0283] Next, the unexposed portions of the curable composition layer are developed and removed to form a pattern (pixels). The unexposed portions of the curable composition layer can be developed and removed using a developer. As a result, the unexposed portions of the curable composition layer in the exposure step are dissolved into the developer, leaving only the photocured portions. The temperature of the developer is preferably, for example, 20 to 30°C. The development time is preferably 20 to 180 seconds. In addition, to improve residue removability, the process of shaking off the developer every 60 seconds and then supplying fresh developer may be repeated several times.

[0284] Examples of the developer include organic solvents and alkaline developers, and alkaline developers are preferably used. Regarding the developer and the washing (rinsing) method after development, the developer and washing method described in paragraph 0214 of WO 2022 / 085485 can be used.

[0285] After development and drying, it is preferable to perform additional exposure treatment or heating treatment (post-baking). The additional exposure treatment or post-baking is a post-development curing treatment to ensure complete curing. The heating temperature in post-baking is, for example, preferably 100 to 300°C, more preferably 200 to 270°C. Post-baking can be performed continuously or batchwise using a heating means such as a hot plate, convection oven (hot air circulation dryer), or high-frequency heater to achieve the above conditions for the developed film. When additional exposure treatment is performed, it is preferable that the light used for exposure has a wavelength of 400 nm or less. The additional exposure treatment may also be performed by the method described in Korean Patent Publication No. 10-2017-0122130.

[0286] <Optical Filter> The film of the present invention can be used in an optical filter. Types of optical filters include color filters, infrared cut filters, and infrared transmission filters, and a color filter is preferred. The color filter preferably has the film of the present invention as its pixel, and more preferably has the film of the present invention as a colored pixel.

[0287] The optical filter may have a protective layer provided on the surface of the film of the present invention. By providing a protective layer, various functions can be imparted, such as oxygen blocking, low reflectivity, hydrophilicity / hydrophobicity, and blocking of light of specific wavelengths (ultraviolet rays, infrared rays, etc.). The thickness of the protective layer is preferably 0.01 to 10 μm, more preferably 0.1 to 5 μm. Methods for forming the protective layer include a method of applying a resin composition for forming the protective layer, a chemical vapor deposition method, and a method of attaching a molded resin with an adhesive. Components constituting the protective layer include (meth)acrylic resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamideimide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, urethane resin, aramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al ２ O ３ , Mo, SiO ２ , Si ２ N ４ For example, in the case of a protective layer intended to block oxygen, the protective layer may contain a polyol resin and SiO ２ and Si ２ N ４ In the case of a protective layer intended to reduce reflection, the protective layer preferably contains a (meth)acrylic resin and a fluorine resin.

[0288] When forming a protective layer by applying a resin composition, known methods such as spin coating, casting, screen printing, and inkjet printing can be used as the method for applying the resin composition. Known organic solvents (e.g., propylene glycol 1-monomethyl ether 2-acetate, cyclopentanone, ethyl lactate, etc.) can be used as the organic solvent contained in the resin composition. When forming the protective layer by chemical vapor deposition, known chemical vapor deposition methods (thermal chemical vapor deposition, plasma chemical vapor deposition, photochemical vapor deposition) can be used as the chemical vapor deposition method.

[0289] The protective layer may contain additives such as organic or inorganic fine particles, absorbers for light of specific wavelengths (e.g., ultraviolet light, infrared light, etc.), refractive index adjusters, antioxidants, adhesives, and surfactants, as needed. Examples of organic or inorganic fine particles include polymeric fine particles (e.g., silicone resin fine particles, polystyrene fine particles, and melamine resin fine particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silica, calcium carbonate, and barium sulfate. Known absorbers for light of specific wavelengths can be used. The content of these additives can be adjusted as appropriate, but is preferably 0.1 to 70% by mass, and more preferably 1 to 60% by mass, of the total mass of the protective layer.

[0290] As the protective layer, the protective layers described in paragraphs 0073 to 0092 of JP-A-2017-151176 can also be used.

[0291] The optical filter may have a structure in which each pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern.

[0292] <Solid-state imaging device> The solid-state imaging device of the present invention has the above-described film of the present invention. The configuration of the solid-state imaging device is not particularly limited as long as it has the film of the present invention and functions as a solid-state imaging device, but examples thereof include the following configurations.

[0293] The substrate includes a plurality of photodiodes constituting a light-receiving area of ​​a solid-state imaging device (such as a CCD (charge-coupled device) image sensor or a CMOS (complementary metal-oxide semiconductor) image sensor) and transfer electrodes made of polysilicon or the like. A light-shielding film is formed on the photodiodes and transfer electrodes, with only the light-receiving portions of the photodiodes exposed. A device protection film made of silicon nitride or the like is formed on the light-shielding film so as to cover the entire light-shielding film and the light-receiving portions of the photodiodes. A color filter is also provided on the device protection film. Furthermore, the device protection film may include a light-collecting means (e.g., a microlens, etc.; the same applies hereinafter) below the color filter (on the side closer to the substrate), or on the color filter. The color filter may have a structure in which each color pixel is embedded in a space partitioned by partition walls, for example, in a grid pattern. In this case, the partition walls preferably have a lower refractive index than the color pixels. Examples of imaging devices having such a structure include those described in JP 2012-227478 A, JP 2014-179577 A, and WO 2018 / 043654 A. Furthermore, as shown in JP 2019-211559 A, an ultraviolet absorbing layer may be provided within the structure of the solid-state imaging element to improve light resistance. An imaging device equipped with the solid-state imaging element of the present invention can be used for digital cameras, electronic devices with imaging functions (such as mobile phones), as well as in-vehicle cameras and surveillance cameras.

[0294] <Image Display Device> The image display device of the present invention has the above-described film of the present invention. Examples of image display devices include liquid crystal display devices and organic electroluminescence display devices. Definitions of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Akio Sasaki, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Nobuaki Ibuki, published by Sangyo Tosho Co., Ltd. in 1989). Liquid crystal display devices are described, for example, in "Next Generation Liquid Crystal Display Technology" (edited by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994). There are no particular limitations on the liquid crystal display device to which the present invention can be applied, and the present invention can be applied to various types of liquid crystal display devices described in the above-mentioned "Next Generation Liquid Crystal Display Technology."

[0295] <Compound, Photosensitizer> The compound of the present invention is a compound represented by the above formula (2a). Furthermore, the photosensitizer of the present invention includes the compound represented by the above formula (2a).

[0296] The present invention will be explained in more detail below with reference to examples. The materials, amounts used, ratios, treatment details, treatment procedures, etc. shown in the following examples can be changed as appropriate without departing from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In addition, in the structural formulas shown below, Me is a methyl group, iPr is an isopropyl group, and Ph is a phenyl group.

[0297] <Synthesis Example> (Method of synthesizing compound (A-1)) 15.9 g of 3-acetylindole and 14.1 g of 4-fluoronitrobenzene were placed in a three-necked flask and dissolved in 500 mL of N,N-dimethylformamide. 50 g of potassium carbonate was added thereto, and the mixture was heated and stirred at 150°C for 6 hours. The resulting reaction solution was added dropwise to 1.5 L of water to cause crystallization, thereby obtaining a crude product of A-1. The crude product was purified by silica gel column chromatography (hexane / ethyl acetate = 8 / 1), thereby obtaining 26.5 g of the target compound (A-1). １ H NMR (CDCl ３ ): 2.50 (s, 3H), 7.35 (dd, 2H), 7.68 (d, 2H), 7.94 (d, 1H), 8.38 (d, 2H), 8.51 (s, 1H), 8.95 (d, 1H)

[0298] (Method for synthesizing compound (A-11)) 40.0 g of indole was added to a three-necked flask and dissolved in 500 mL of chlorobenzene. After cooling to 5°C, 98 g of tin tetrachloride was added, and 57.0 g of 3-cyclopentylpropionyl chloride was added dropwise over 30 minutes. The reaction solution was stirred at room temperature for an additional hour, and then added to 1.5 L of ice water to terminate the reaction. The resulting solid was filtered and recrystallized from methanol to obtain 43.5 g of the target compound (A-11). １ H NMR (CDCl ３): 1.18 (m, 2H), 1.52 (m, 2H), 1.65 (m, 2H), 1.81 (m, 5H), 2.91 (dd, 2H), 7.28 (d, 2H), 7.42 (d, 1H), 7.89 (s, 1H), 8.42 (d, 1H), 8.92 (brs, 1H)

[0299] (Method for synthesizing compound (A-12)) 40.0 g of indole was added to a three-necked flask and dissolved in 500 mL of chlorobenzene. After cooling to 5°C, 100 mL of a 50% aqueous sodium hydroxide solution and 33.6 g of acetyl chloride were added and stirred for 4 hours. The organic layer of the reaction solution was separated, and then 98 g of tin tetrachloride was added, followed by dropwise addition of 57.0 g of 3-cyclopentylpropionyl chloride over 30 minutes. The reaction solution was stirred at room temperature for an additional hour and then added to 1.5 L of ice water to terminate the reaction. The resulting solid was filtered and recrystallized from methanol to obtain 49.7 g of the target compound (A-12). １ H NMR (CDCl ３ ): 1.18 (m, 2H), 1.52 (m, 2H), 1.65 (m, 2H), 1.81 (m, 5H), 2.20 (s, 3H), 2.91 (dd, 2H), 7.28 (d, 2H), 7.42 (d, 1H), 7.79 (s, 1H), 8.42 (d, 1H)

[0300] (Method for synthesizing compound (A-13)) 53.1 g of the target compound (A-13) was obtained in the same manner as in the synthesis of compound (A-12), except that benzoyl chloride was used instead of acetyl chloride. １ H NMR (CDCl ３ ): 1.18 (m, 2H), 1.52 (m, 2H), 1.65 (m, 2H), 1.81 (m, 5H), 2.91 (dd, 2H), 7.28 (d, 2H), 7.42 (d, 1H), 7.61 (d, 2H), 7.73 (t, 1H), 7.79 (s, 1H), 7.85 (d, 1H), 8.11 (d, 1H), 8.42 (d, 1H)

[0301] (Method for Synthesizing Compound (A-18)) 41.5 g of intermediate (A-18a) was obtained in the same manner as in the synthesis of compound (A-11), except that 4-methylvaleroyl chloride was used instead of 3-cyclopentylpropionic acid chloride. 21.5 g of intermediate (A-18a) and 20.0 g of 4-fluorobenzophenone were placed in a three-neck flask and dissolved in 500 mL of N,N-dimethylformamide. 17.8 g of tripotassium phosphate was added to the mixture, and the mixture was heated and stirred at 110°C for 24 hours. The resulting reaction solution was crystallized in 1.5 L of a mixture of methanol and distilled water (volume ratio (50 vol / 50 vol)), and the resulting powder was collected by filtration. The mixture was purified by recrystallization from methanol, yielding 37.9 g of the target compound (A-18). １ H NMR (CDCl ３ ): 0.91 (d, 6H), 1.52 (m, 3H), 2.97 (dd, 2H), 7.28 (d, 2H), 7.42 (d, 1H), 7.89 (s, 1H), 8.42 (d, 1H), 8.92 (brs, 1H)

[0302] (Method for synthesizing compound (A-19)) 39.8 g of the target compound (A-19) was obtained in the same manner as in the synthesis of compound (A-18), except that compound (A-11) was used instead of intermediate (A-18a). １ H NMR (DMSO (dimethyl sulfoxide)): 1.14 (m, 2H), 1.49 (m, 2H), 1.59 (m, 2H), 1.6-1.9 (m, 5H), 2.98 (t, 2H), 7.34 (m, 2H), 7.62 (t, 2H), 7.71 (m, 2H), 7.83 (d, 2H), 7.91 (d, 2H), 7.99 (d, 2H), 8.38 (m, 1H), 8.77 (s, 1H)

[0303] (Method for synthesizing compound (A-25)) 32.3 g of the target compound (A-25) was obtained in the same manner as in the synthesis of compound (A-19), except that 4-fluoronitrobenzene was used instead of 4-fluorobenzophenone. １ H NMR (CDCl ３): 1.16 (m, 2H), 1.50 (m, 2H), 1.63 (m, 2H), 1.81 (m, 5H), 2.89 (dd, 2H), 7.35 (dd, 2H), 7.68 (d, 2H), 7.94 (d, 1H), 8.38 (d, 2H), 8.51 (s, 1H), 8.95 (d, 1H)

[0304] (Method for synthesizing compound (A-52)) 38.5 g of the target compound (A-52) was obtained in the same manner as in the synthesis of compound (A-19), except that (4-fluorophenyl)(4-(methylthio)naphthalen-1-yl)methanone was used instead of 4-fluorobenzophenone. １ H NMR (CDCl ３ ): 1.16 (m, 2H), 1.50 (m, 2H), 1.63 (m, 2H), 1.81 (m, 5H), 2.93 (dd, 2H), 4.09 (s, 3H), 6.84 (d, 1H), 7.35 (m, 2H), 7.5-7.7 (m, 5H), 8.00 (s, 1H), 8.04 (d, 2H), 8.38 (d, 1H), 8.42 (d, 1H), 8.49 (d, 1H)

[0305] (Method for Synthesizing Compound (A-55)) Compound (A-55) was synthesized according to the synthesis scheme shown below. That is, 1-methoxynaphthalene was subjected to Friedel-Crafts reaction in the presence of a Lewis acid to obtain intermediate (A-55-a) having an F atom. Next, indole was acetyl-protected, and then acylated by a metal-free Friedel-Crafts type reaction using a Bronsted acid in an exchange anhydride method, followed by deprotection of the acetyl group to obtain intermediate (A-55-b). Finally, intermediate (A-55-a) and intermediate (A-55-b) were coupled by aromatic nucleophilic substitution reaction (SNAr reaction) in the presence of a base to obtain compound (A-55). Details of the synthesis methods for intermediate (A-55-a), intermediate (A-55-b), and compound (A-55) are shown below.

[0306] -Synthesis of Intermediate (A-55-a)- Under a nitrogen atmosphere, 15.8 g of 1-methoxynaphthalene was added to a three-neck flask and dissolved in 200 mL of chlorobenzene. After cooling this solution to 5°C, 14.2 g of aluminum chloride was added and the mixture was stirred at 5°C for an additional 30 minutes. To this reaction solution, 50 mL of a chlorobenzene solution containing 15.9 g of 4-fluorobenzoyl chloride was added dropwise over 30 minutes and the mixture was stirred at a temperature of 5-10°C for 1 hour. The mixture was then heated to 25°C and stirred for an additional 2 hours. The resulting reaction solution was slowly added dropwise to a crystallization solution of 600 mL of methanol and 400 mL of 1N hydrochloric acid cooled to 0°C, and the resulting crystals were collected by filtration. The collected crystals were washed with methanol cooled to 5°C and dried to obtain 26.6 g of intermediate (A-55-a) (yield 95%). １ H NMR (CDCl ３ ): 3.76 (s, 3H), 6.45 (d, 1H), 7.39 (d, 2H), 7.61 (t, 1H), 7.76 (t, 1H), 7.79 (d, 2H), 8.05 (d, 1H), 8.38 (d, 1H), 9.12 (d, 1H)

[0307] —Synthesis of Intermediate (A-55-b)— Under a nitrogen atmosphere, 11.7 g of indole was added to a three-neck flask and dissolved in 100 mL of toluene. To this was added a mixed alkaline solution of 5.6 g of potassium hydroxide and 80 mL of water, and 3.8 g of tetrabutylammonium bromide was added. The resulting two-layer reaction solution was maintained at 25°C with slow stirring, and 7.9 g of acetyl chloride was added dropwise over 10 minutes, followed by further stirring at 25°C for 1 hour. After confirming the disappearance of the starting indole by thin layer chromatography (TLC), stirring was promptly stopped, and the alkaline layer, which had separated into two layers, was separated and removed. 100 mL of saturated aqueous ammonium chloride solution was added to this, and after further stirring for 30 minutes, the aqueous layer was removed, and the resulting organic layer was concentrated. Under a nitrogen atmosphere, the concentrate of the organic layer obtained above was diluted with 100 mL of toluene in a three-neck flask and cooled to 5°C. To this was added 16.7 g of 3-cyclohexylpropionic acid, followed by 30 mL of trifluoroacetic acid and 30 mL of trifluoroacetic anhydride, and the mixture was stirred at 5°C for an additional 30 minutes. Next, 19.2 g of methanesulfonic acid was added dropwise over 30 minutes, the mixture was heated to 25°C, and the mixture was stirred for an additional 4 hours. After confirming the disappearance of the starting material N-acetylindole by TLC, the resulting reaction solution was cooled again to 5°C, and 100 mL of water was added dropwise over 1 hour. The aqueous layer was separated and removed, and 35 g of tripotassium phosphate and 100 mL of water were added to the resulting organic layer and separated to obtain an organic layer. Under a nitrogen atmosphere, the organic layer obtained above was added to a three-neck flask, and 100 mL of 1N aqueous sodium hydroxide solution was added, followed by heating and stirring at 50°C for 2 hours. After confirming the disappearance of the starting material N-acetyl-3-(3-cyclohexylcarbonyl)indole by TLC, the alkaline aqueous layer was removed by separation, the mixture was cooled to 5°C, and 50 mL of acetic acid was added dropwise. The resulting crystals were collected by filtration, washed with 100 mL of cold water, and then washed with 50 mL of cold methanol to obtain 21.7 g (yield 85%) of intermediate (A-55-b) as white crystals. １ HNMR (DMSO): 1.1-1.9 (m, 13H), 2.91 (t, 2H), 7.26 (m, 2H), 7.41 (d, 1H), 7.89 (s, 1H), 8.42 (d, 1H), 8.69 (brs, 1H)

[0308] - Synthesis of Compound (A-55) - 14.0 g of intermediate (A-55-a) and 17.0 g of intermediate (A-55-b) obtained above were placed in a three-neck flask under a nitrogen atmosphere and dissolved in 200 mL of N,N-dimethylacetamide. 18.5 g of tripotassium phosphate was added, and the mixture was heated and stirred at 130°C for 24 hours. The disappearance of the raw materials, intermediate (A-55-a) and intermediate (A-55-b), was confirmed by TLC, and the resulting reaction solution was allowed to cool to 25°C. The reaction solution was slowly added dropwise to 500 mL of methanol and 500 mL of ethylene glycol cooled to 5°C, and the resulting solid was filtered as a crude product. This crude product was then reslurried in 500 mL of methanol and 500 mL of water cooled to 5°C for 1 hour, and the purified solid was collected by filtration and further washed three times with 100 mL of methanol cooled to 5°C. In this way, 23.7 g (yield 92%) of compound (A-55) was obtained. １ H NMR (CDCl ３ ): 1.1-1.9 (m, 13H), 2.33 (s, 3H), 2.87 (dd, 2H), 4.09 (s, 3H), 6.84 (d, 1H), 7.34 (m, 2H), 7.63 (m, 7H), 8.03 (d, 2H), 8.39 (t, 2H), 8.48 (dd, 1H)

[0309] (Method for synthesizing compound (A-65)) 36.6 g of the target compound (A-65) was obtained in the same manner as in the synthesis of compound (A-19), except that (9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl)(4-fluoro-2-methylphenyl)methanone was used instead of 4-fluorobenzophenone. １ H NMR (CDCl ３ ): 1.16 (m, 2H), 1.37 (t, 3H), 1.50 (m, 2H), 1.63 (m, 2H), 1.81 (m, 5H), 2.38 (s, 3H), 2.48 (s, 3H) 2.93 (dd, 2H), 4.33 (q, 2H), 7.0-9.0 (m, 18H)

[0310] (Method for synthesizing compound (A-66)) 34.1 g of the target compound (A-66) was obtained in the same manner as in the synthesis of compound (A-19), except that (8-(4-fluoro-2-methylbenzoyl)dibenzo[b,d]thiophen-2-yl)(o-tolyl)methanone was used instead of 4-fluorobenzophenone. １ H NMR (CDCl ３ ): 1.19 (m, 2H), 1.55 (m, 2H), 1.64 (m, 2H), 1.85 (m, 5H), 2.36 (s, 3H), 2.50 (s, 3H), 2.96 (dd, 2H), 7.2-7.7 (m, 13H), 8.00 (d, 1H), 8.05 (s, 1H), 8.12 (d, 1H), 8.48 (m, 3H)

[0311] (Method for synthesizing compound (A-67)) 32.5 g of the target compound (A-67) was obtained in the same manner as in the synthesis of compound (A-19), except that (8-(4-fluoro-2-methylbenzoyl)dibenzo[b,d]furan-2-yl)(o-tolyl)methanone was used instead of 4-fluorobenzophenone. １ H NMR (CDCl ３ ): 1.19 (m, 2H), 1.55 (m, 2H), 1.64 (m, 2H), 1.85 (m, 5H), 2.36 (s, 3H), 2.50 (s, 3H), 2.96 (dd, 2H), 7.2-7.7 (m, 13H), 8.08 (d, 1H), 8.11 (s, 1H), 8.19 (d, 1H), 8.38 (m, 3H)

[0312] (Method for synthesizing compound (A-79)) 8.9 g of p-toluenesulfonyl chloride was added to a three-necked flask and dissolved in 500 mL of tetrahydrofuran. After cooling to 5°C, a solution of 12.3 g of compound (A-11) and 4.3 g of N,N-dimethylaminopyridine in 100 mL of tetrahydrofuran was added dropwise over 20 minutes. The reaction solution was heated to 25°C and then stirred for an additional 2 hours. 500 mL of ethyl acetate and 500 mL of pure water were added to the reaction solution, and the organic layer was washed and concentrated. The concentrate was purified by silica gel column chromatography (hexane / ethyl acetate = 10 / 1) to obtain 9.8 g of the target compound (A-79). １ H NMR (CDCl３ ): 1.18 (m, 2H), 1.52 (m, 2H), 1.65 (m, 2H), 1.81 (m, 5H), 2.35 (s, 3H), 2.91 (dd, 2H), 7.28 (d, 2H), 7.42 (d, 1H), 7.44 (d, 2H), 7,75 (d, 2H), 7.89 (s, 1H), 8.42 (d, 1H)

[0313] (Method for synthesizing compound (A-80)) 29.8 g of the target compound (A-80) was obtained in the same manner as in the synthesis of compound (A-19), except that (9,9-dimethyl-7-nitro-9H-fluoren-2-yl)(4-fluoro-2-methylphenyl)methanone was used instead of 4-fluorobenzophenone. １ H NMR (CDCl ３ ): 1.18 (m, 2H), 1.54 (m, 2H), 1.63 (m, 2H), 1.69 (s, 6H), 1.84 (m, 5H), 2.49 (s, 3H), 2.97 (dd, 2H), 7.1-7.7 (m, 10H), 8.16 (s, 1H), 8.31 (d, 1H), 8.48 (s, 1H), 8.95 (d, 1H)

[0314] Compounds (A-1) to (A-80) are compounds having the structures shown below.

[0315] <Preparation of Dispersion> A mixture of the materials listed in the table below was mixed and dispersed for 3 hours using a bead mill (zirconia beads 0.1 mm in diameter). Then, a high-pressure disperser with a pressure reduction mechanism (NANO-3000-10, manufactured by Nippon BEE Co., Ltd.) was used to mix and disperse the mixture at a pressure of 2000 kg / cm. ２ and a flow rate of 500 g / min. This dispersion process was repeated 10 times to obtain a dispersion. When two or more materials are listed in the "Type" column of the table, the total amount of each material, using equal amounts, is listed in the "Parts by mass" column.

[0316]

[0317]

[0318]

[0319] Details of the raw materials listed by abbreviations in the table above are as follows:

[0320] (Coloring materials) PR254: C.I. Pigment Red 254 (diketopyrrolopyrrole compound, red pigment) PR272: C.I. Pigment Red 272 (diketopyrrolopyrrole compound, red pigment) PR291: C.I. Pigment Red 291 (brominated diketopyrrolopyrrole compound, red pigment) PR177: C.I. Pigment Red 177 (anthraquinone compound, red pigment) PR264: C.I. Pigment Red 264 (diketopyrrolopyrrole compound, red pigment) PG36: C.I. Pigment Green 36 (copper phthalocyanine compound, green pigment) PG58: C.I. Pigment Green 58 (zinc phthalocyanine compound, green pigment) PY129: C.I. Pigment Yellow 129 (azomethine copper complex, yellow pigment) PY138: C.I. Pigment Yellow 138 (quinophthalone compound, yellow pigment) PY139: C.I. Pigment Yellow 139 (isoindoline compound, yellow pigment) PY150: C.I. Pigment Yellow 150 (monoazo compound, yellow pigment) PY185: C.I. Pigment Yellow 185 (isoindoline compound, yellow pigment) PY215: C.I. Pigment Yellow 215 (Pritedin compound, yellow pigment) PB15:6: C.I. Pigment Blue 15:6 (copper phthalocyanine compound, blue pigment) PV23: C.I. Pigment Violet 23 (dioxazine compound, purple pigment) P-1: Compound of the following structure (pyrrolopyrrole compound, infrared absorbing colorant) P-2: Compound having the following structure (squarylium compound, infrared absorbing colorant) P-3: Titanium black (TiOxNy, manufactured by Mitsubishi Materials Corporation, black pigment) P-4: Titanium oxide (TTO-51(C), manufactured by Ishihara Sangyo Kaisha, Ltd., white pigment) P-5: Compound having the following structure (xanthene magenta dye)

[0321] (Dispersing aid) Syn-1: Compound having the following structure Syn-2: a compound having the following structure Syn-3: Compound having the following structure (a / b / c=10 / 70 / 20 (mol %), weight average molecular weight: 600) Syn-5: a compound having the following structure Syn-6: a compound having the following structure Syn-7: a compound having the following structure

[0322] (Resin) C2-1: Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 20,000, acid value: 67 mgKOH / g) C2-2: Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 23,000, acid value: 59 mg KOH / g) C2-3: Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 18,000, acid value: 69 mg KOH / g) C2-4: Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight average molecular weight: 23,000, acid value: 67 mg KOH / g) C2-5: Resin having the following structure (weight average molecular weight 10,000, acid value 85 mgKOH / g) C2-6: Resin having the following structure (weight average molecular weight 18,000, acid value 82 mgKOH / g)

[0323] (Solvent) S-1: Propylene glycol monomethyl ether acetate S-2: Propylene glycol monomethyl ether S-3: Cyclohexanone S-4: Equal mixture of 3-methoxypropanol and butyl acetate

[0324] <Preparation of curable compositions> The dispersions obtained above were mixed with the materials shown in the table below in the parts by mass shown in the table below, and the mixture was stirred and then filtered through a nylon filter having a pore size of 0.45 μm (manufactured by Nippon Pall Co., Ltd.), to prepare curable compositions. The entire amount of each dispersion obtained above was used.

[0325]

[0326]

[0327]

[0328]

[0329]

[0330] Details of the materials indicated by the abbreviations in the table are as follows:

[0331] (Dispersions) Dispersions 1 to 89, Dispersions C1 to C3: Dispersions 1 to 89, Dispersions C1 to C3 described above

[0332] (Resin) B-1: Resin having the following structure (the numerical values ​​attached to the main chain are molar ratios; weight average molecular weight: 11,000; acid value: 69 mg KOH / g) B-2: Resin having the following structure (the number attached to the main chain is the molar ratio, and the number attached to the side chain is the number of repeating units. Weight-average molecular weight: 21,000) B-3: Resin having the following structure (the numbers attached to the main chain are molar ratios; weight average molecular weight: 12,000; acid value: 80 mg KOH / g)

[0333] (Polymerizable Compound) M-1: A mixture of compounds having the following structure (a mixture of the compound on the left (a hexafunctional (meth)acrylate compound) and the compound on the right (a pentafunctional (meth)acrylate compound) in a molar ratio of 7:3) M-2: Compound of the following structure M-3: Compound having the following structure M-4: Compound having the following structure M-5: Compound having the following structure

[0334] (Photosensitizers) A-1 to A-4, A-7 to A-21, A-26 to A-28, A-32, A-33, A-35, A-39, A-55 to A-78, A-80: the above-mentioned compounds A-1 to A-4, A-7 to A-21, A-26 to A-28, A-32, A-33, A-35, A-39, A-55 to A-78, A-80 cA-1: Compound of the following structure (comparative compound)

[0335] (Photopolymerization initiators) I-1 to I-12: Compounds having the following structures

[0336] (Additives) T-1 to T-6: Compounds having the following structures

[0337] (Solvent) S-1: Propylene glycol monomethyl ether acetate S-2: Propylene glycol monomethyl ether S-3: Cyclohexanone S-4: Equal mixture of 3-methoxypropanol and butyl acetate

[0338] <Evaluation> (Sensitivity Evaluation) CT-4000L (manufactured by FUJIFILM Electronic Materials Co., Ltd.) was applied to an 8-inch (20.32 cm) silicon wafer using a spin coater so that the thickness after post-baking would be 0.1 μm, and the wafer was heated on a hot plate at 220°C for 300 seconds to form an undercoat layer, thereby obtaining a silicon wafer with an undercoat layer. Each of the curable compositions obtained above was applied by spin coating onto the undercoat layer of the silicon wafer with an undercoat layer so that the film thickness after application would be 0.6 μm, and then the wafer was heated on a hot plate at 100°C for 2 minutes to form a composition layer. Next, the obtained composition layer was exposed to light (KrF radiation) with a wavelength of 248 nm through a mask having a 0.5 μm square pattern using a KrF scanner exposure machine at an illuminance of 35,000 W / m ２ , pulse width 20 nanoseconds, frequency 50 kHz, exposure dose 20 mJ / cm ２ ~300 mJ / cm ２The exposure was carried out by changing the irradiation amount within the range. Next, the composition layer after exposure was subjected to shower development at 23°C for 60 seconds using a 0.3 mass% aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer. Thereafter, water droplets adhering to the pattern surface were removed with air, and the pattern was allowed to dry naturally to form a pattern (pixels). The silicon wafer on which pixels had been formed was observed at a magnification of 20,000 times using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Technologies Corporation). The exposure amount required for the pattern line width to reach 0.6 μm in the observed pixels was calculated, and the exposure sensitivity was evaluated according to the following evaluation criteria. -Evaluation criteria- A: Exposure amount was 20 mJ / cm ２ B: The exposure amount is 20 mJ / cm or less ２ exceeding 30 mJ / cm ２ C: The exposure amount is 30 mJ / cm or less ２ exceeding 50 mJ / cm ２ D: The exposure amount is 50 mJ / cm or less ２ exceeding 100 mJ / cm ２ E: The exposure amount is 100 mJ / cm or less ２ exceed

[0339] <Evaluation of Adhesion> Each of the curable compositions obtained above was applied by spin coating onto the undercoat layer of the undercoat-layer-attached silicon wafer so that the film thickness after application would be 0.6 μm, and then heated at 100° C. for 2 minutes using a hot plate to form a composition layer. Next, using a KrF scanner exposure machine, the obtained composition layer was irradiated with light (KrF rays) with a wavelength of 248 nm through a mask engraved with a 0.6 μm checkered pattern at an illuminance of 35,000 W / m ２ , pulse width 20 nanoseconds, frequency 50 kHz, exposure dose 30 mJ / cm ２The composition layer was then exposed to light at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as the developer. The exposed composition layer was then subjected to puddle development at 23°C for 60 seconds. The layer was then rinsed with pure water for 20 seconds using a spin shower, and then washed with pure water. Water droplets adhering to the pattern surface were then removed with air, and the pattern was allowed to dry naturally to form a pattern (pixels). The silicon wafer with the formed pixels was observed at a magnification of 20,000 times using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Technologies Corporation). The ratio of missing pixels among 100 pixels was observed from the scanning electron microscope photograph to evaluate adhesion. The evaluation criteria are as follows: -Evaluation criteria- A: The ratio of missing pixels is 0% B: The ratio of missing pixels is more than 0% but not more than 10% C: The ratio of missing pixels is more than 10% but not more than 20% D: The ratio of missing pixels is more than 20% but not more than 50% E: The ratio of missing pixels is more than 50%

[0340] (Evaluation of Roughness of Pixel Sidewall Portion) The silicon wafer on which the pixels formed in the above adhesion evaluation were formed was cut, and the pixel cross section was observed for line width using a scanning electron microscope, and the variation in pixel line width at a line width of 0.6 μm in the pattern was observed. Specifically, using a length measurement scanning electron microscope, the pixel line width was detected at multiple positions (10 positions in total) in a measurement monitor, and the variance (3σ) of the variation in the detected positions was used as an index of the roughness of the pixel sidewall portion. -Evaluation Criteria- A: 3σ is 1% or less of the pattern line width B: 3σ is more than 1% and 2% or less of the pattern line width C: 3σ is more than 2% and 3% or less of the pattern line width D: 3σ is more than 3% and 5% or less of the pattern line width E: 3σ is more than 5% of the pattern line width

[0341]

[0342]

[0343] As shown in the above table, the curable compositions of the examples were excellent in the evaluations of sensitivity and adhesion.

[0344] The films obtained from the curable compositions of the examples can be suitably used in solid-state imaging devices and image display devices.

Claims

1. A curable composition comprising a photopolymerization initiator, a polymerizable compound, and a compound represented by formula (1); In formula (1), R １ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group; R ２ represents an alkyl group, an aryl group, or a heteroaryl group; R ３ ~R ７ each independently represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; R ４ ~R ７ Adjacent groups among these may be bonded to form a ring.

2. The curable composition according to claim 1, wherein the compound represented by formula (1) is a compound represented by formula (2): In formula (2), R ２１ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group; L ２１ represents a single bond or an alkylene group; R ２２ａ and R ２２ｂ each independently represents an alkyl group; R ２２ａ and R ２２ｂ may be bonded to form a ring, R ２３ ~R ２７ each independently represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; R ２４ ~R ２７ Adjacent groups among these may be bonded to form a ring.

3. The curable composition according to claim 1, wherein the compound represented by formula (1) is a compound represented by formula (3). In formula (3), R ３１ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group; L ３１ represents a single bond or an alkylene group having 1 to 4 carbon atoms; ３２ Ha- (CR Ｌ１ R Ｌ２ ) ｐ - represents R Ｌ１ and R Ｌ２ each independently represents a hydrogen atom or an alkyl group, p represents an integer of 1 to 5, R ３２ａ and R ３２ｂ each independently represents a hydrogen atom or an alkyl group; R ３３ ~R ３７ each independently represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; R ３４ ~R ３７ Adjacent groups among these may be bonded to form a ring.

4. The curable composition according to claim 1, wherein the compound represented by formula (1) is a compound represented by formula (4). In formula (4), R ４１ represents a hydrogen atom, a halogen atom, a nitro group or an acyl group; R ４２ represents an alkyl group, an aryl group or a halogen atom; R ４３ ~R ４７ each independently represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; R ４４ ~R ４７ adjacent groups may be bonded to each other to form a ring; and m represents an integer of 0 to 4.

5. The curable composition according to any one of claims 1 to 4, comprising 0.01 to 500 parts by mass of based on 100 parts by mass of the photopolymerization initiator.

6. The curable composition according to any one of claims 1 to 4, wherein the photopolymerization initiator comprises an oxime compound having an indole skeleton.

7. The curable composition according to any one of claims 1 to 4, further comprising a coloring material.

8. The curable composition according to any one of claims 1 to 4, further comprising an amine compound.

9. The curable composition according to any one of claims 1 to 4, further comprising a chain transfer agent.

10. A method for manufacturing a pixel, comprising the steps of: forming a curable composition layer on a support using the curable composition according to any one of claims 1 to 4; exposing the curable composition layer to light having a wavelength of 150 to 300 nm in a pattern; and developing and removing the unexposed areas of the curable composition layer.

11. A film obtained by curing the curable composition according to any one of claims 1 to 4.

12. A solid-state imaging device comprising the film according to claim 11.

13. An image display device comprising the film according to claim 11.

14. A compound represented by formula (2a); In formula (2a), R ２１ａ represents a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, an acyl group, an alkylsulfonyl group or an arylsulfonyl group; L ２１ａ represents an alkylene group having 1 to 4 carbon atoms; R ２２Ｌａ and R ２２Ｌｂ each independently represents an alkyl group; R ２２Ｌａ and R ２２Ｌｂ may be bonded to form a ring, R ２３ａ ~R ２７ａ each independently represents a hydrogen atom, a halogen atom, a nitro group, or a monovalent organic group; R ２４ａ ~R ２７ａ Adjacent groups among these may be bonded to form a ring.

15. A photosensitizer comprising the compound of claim 14.

Images