Curable composition, method for producing cured product, film, optical element, image sensor, solid-state imaging element, and image display device

Abstract

A curable composition, a method for producing a cured product of the curable composition, a method for producing a cured product using the curable composition, a film, an optical element, an image sensor, a solid-state imaging element, or an image display device. The curable composition includes a compound in which an indole skeleton is directly linked to an oxime group or a ketoxime group, a radical curable compound, and a resin including a resin having a graft chain and a crosslinkable group.

Description

Technical Field

[0001] The present invention relates to a curable composition, a method for producing a cured product, a film, an optical element, an image sensor, a solid-state imaging element, and an image display device. Background Art

[0002] An optical filter such as a color filter is produced using a curable composition containing a colorant, a photopolymerization initiator, and a polymerizable compound.

[0003] As conventional curable compositions, compositions described in the following Patent Documents 1 and 2 are known.

[0004] The following Patent Documents 1 and 2 each describe a composition containing an oxime ester compound having an indole nucleus.

[0005] Patent Document 1: Japanese Patent Application Laid-Open No. 2021-173858

[0006] Patent Document 2: Japanese Patent Application Laid-Open No. 2021-167893 Summary of the Invention

[0007] Technical issues to be solved by the invention

[0008] An object of the embodiments of the present invention is to provide a highly sensitive curable composition.

[0009] Another embodiment of the present invention aims to provide a method for producing a cured product using the curable composition, a film, an optical element, an image sensor, a solid-state imaging element, or an image display device.

[0010] Means for solving technical problems

[0011] Means for solving the above-mentioned problems include the following.

[0012] <1> A curable composition comprising:

[0013] Compounds in which an indole skeleton is directly linked to an oxime group or a ketoxime group;

[0014] Free radical curable compounds; and

[0015] Resin,

[0016] The above-mentioned resin includes a resin having a graft chain and a crosslinking group.

[0017] <2> according to <1> The curable composition, wherein

[0018] The compound in which the indole skeleton is directly linked to an oxime group or a ketoxime group is a compound represented by the following formula (1).

[0019] [Chemical Formula 1]

[0020]

[0021] In formula (1), R1 represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group or a heteroaryloxy 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 or a monovalent organic group, Ar represents an aryl group or a heteroaryl group, and n represents 0 or 1.

[0022] <3> according to <2> The curable composition, wherein

[0023] The Ar in the above formula (1) is a group represented by the following formula (2).

[0024] [Chemical Formula 2]

[0025]

[0026] In formula (2), Ar1 and Ar2 each independently represent an arylene group or a heteroarylene group, and R 21 Each independently represents a halogen atom or a monovalent organic group, m represents an integer of 0 to 5, and * represents a bonding portion to the nitrogen atom of the indole ring.

[0027] <4> according to <1> ~ <3> The curable composition according to any one of the preceding claims, wherein

[0028] The compound in which an indole skeleton is directly linked to an oxime group or a ketoxime group is a mixture of a compound having one oxime group or a ketoxime group in one molecule and a compound having two or more oxime groups or a ketoxime group in one molecule.

[0029] <5> according to <1> ~ <4> The curable composition according to any one of the preceding claims, further comprising a polyfunctional thiol compound.

[0030] <6> according to <1> ~ <5> The curable composition according to any one of the preceding claims, wherein

[0031] The resin having the graft chain and the crosslinking group is an acrylic resin.

[0032] <7> according to <1> ~ <6> The curable composition according to any one of the preceding claims, wherein

[0033] The resin having the graft chain and the crosslinkable group further has at least one group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

[0034] <8> according to <1> ~ <7> The curable composition according to any one of the preceding claims, wherein

[0035] The crosslinkable group is at least one group selected from the group consisting of an ethylenically unsaturated group and a cyclic ether group.

[0036] <9> according to <1> ~ <8> The curable composition according to any one of the preceding claims, wherein

[0037] The content of the radical-curable compound having a molecular weight of less than 3000 among the radical-curable compounds is less than 15% by mass based on the total solid content.

[0038] <10> according to <9> The curable composition, wherein

[0039] When the mass of the radical curable compound having a molecular weight of less than 3000 is defined as W1 and the mass of the compound in which the indole skeleton is directly linked to an oxime group or a ketoxime group is defined as W2, W1 / W2<5 is satisfied.

[0040] <11> according to <1> to <10> The curable composition according to any one of the preceding claims, further comprising a colorant.

[0041] <12> A method for producing a solidified product, comprising: <1> to <11> a step of irradiating the curable composition according to any one of the preceding claims with an excimer laser having a wavelength of 150 nm to 300 nm.

[0042] <13> A membrane formed by <1> to <11> The curable composition described in any one of the above is cured.

[0043] <14> An optical element comprising <13> The membrane.

[0044] <15> An image sensor comprising <13> The membrane.

[0045] <16> A solid-state imaging element comprising <13> The membrane.

[0046] <17> An image display device comprising <13> The membrane.

[0047] Effects of the Invention

[0048] According to an embodiment of the present invention, a highly sensitive curable composition is provided.

[0049] Furthermore, according to another embodiment of the present invention, there is provided a method for producing a cured product using the curable composition, a film, an optical element, an image sensor, a solid-state imaging element, or an image display device. DETAILED DESCRIPTION

[0050] The following description of the components is based on representative embodiments of the present invention, but the present invention is not limited to these embodiments.

[0051] In this specification, “to” is used to mean that the numerical values ​​described before and after it are inclusive as the lower limit and the upper limit.

[0052] In the description of groups (atomic groups) in this specification, expressions not marked with "substituted" or "unsubstituted" include groups (atomic groups) without substitution and groups (atomic groups) with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0053] In this specification, "exposure" includes not only exposure using light, but also drawing using particle beams such as electron beams and ion beams, unless otherwise specified. Examples of light used for exposure include active light or radiation such as the bright line spectrum of a mercury lamp, far ultraviolet light represented by excimer lasers, extreme ultraviolet light (EUV light), X-rays, and electron beams.

[0054] In this specification, “(meth)acrylate” means both or either acrylate and methacrylate, “(meth)acrylic acid” means both or either acrylic acid and methacrylic acid, and “(meth)acryloyl” means both or either acryloyl and methacryloyl.

[0055] In the present specification, Me in the structural formula represents a methyl group, Et represents an ethyl group, Bu represents a butyl group, and Ph represents a phenyl group.

[0056] In this specification, the weight average molecular weight and the number average molecular weight are polystyrene-equivalent values ​​measured by GPC (gel permeation chromatography).

[0057] In this specification, the total solid content refers to the total mass of the components excluding the solvent from all the components of the composition.

[0058] In this specification, a pigment refers to a colorant that is not easily soluble in a solvent.

[0059] In this specification, the term "step" includes not only independent steps but also steps that cannot be clearly distinguished from other steps as long as the intended effect of the step is achieved.

[0060] In the present specification, oxime compounds that exist as E-isomers and Z-isomers may be either the E-isomer or the Z-isomer unless otherwise specified.

[0061] Hereinafter, the present invention will be described in detail.

[0062] (Curable composition)

[0063] The curable composition of the present invention comprises: a colorant; a compound having an indole skeleton directly linked to an oxime group or a ketoxime group (hereinafter also referred to as compound (A)); a radical curable compound; and a resin having a graft chain and a crosslinking group.

[0064] As a result of intensive studies, the present inventors have found that a highly sensitive curable composition can be obtained by adopting the above-mentioned configuration.

[0065] The indole skeleton of compound (A) sharpens its light absorption peak, enhancing light absorption efficiency. Furthermore, the direct bonding of the (keto)oxime ester structure to the indole skeleton promotes the generation of free radicals from the (keto)oxime ester structure. Furthermore, by including a resin having a graft chain and a crosslinking group along with compound (A), the resin having the graft chain and the crosslinking group effectively captures and polymerizes free radical polymerization initiating species generated by compound (A), presumably resulting in a highly sensitive curable composition.

[0066] The curable composition of the present invention can be preferably used as a photocurable composition, more preferably as a curable composition for exposure to light with a wavelength of 150 nm to 300 nm, and particularly preferably as a curable composition for excimer laser exposure with a wavelength of 150 nm to 300 nm.

[0067] Furthermore, the curable composition of the present invention can be preferably used as a curable composition for optical filters. As optical filters, color filters and infrared transmission filters can be mentioned, preferably color filters. That is, the curable composition of the present invention can be preferably used as a curable composition for color filters. More specifically, it can be preferably used as a curable composition for pixel formation of a color filter. As the type of pixel, red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc. can be mentioned.

[0068] Preferred examples of infrared transmission filters include filters that satisfy spectral characteristics such that the maximum transmittance within the wavelength range of 400 nm to 640 nm is 20% or less (preferably 15% or less, more preferably 10% or less), and the minimum transmittance within the wavelength range of 1,100 nm to 1,300 nm is 70% or more (preferably 75% or more, more preferably 80% or more). The infrared transmission filter preferably satisfies any of the following spectral characteristics (1) to (5).

[0069] (1) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) within a wavelength range of 400 nm to 640 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) within a wavelength range of 800 nm to 1,500 nm.

[0070] (2) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) within a wavelength range of 400 nm to 750 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) within a wavelength range of 900 nm to 1,500 nm.

[0071] (3) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) within a wavelength range of 400 nm to 830 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) within a wavelength range of 1,000 nm to 1,500 nm.

[0072] (4) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) within a wavelength range of 400 nm to 950 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) within a wavelength range of 1,100 nm to 1,500 nm.

[0073] (5) A filter having a maximum transmittance of 20% or less (preferably 15% or less, more preferably 10% or less) within a wavelength range of 400 nm to 1,050 nm and a minimum transmittance of 70% or more (preferably 75% or more, more preferably 80% or more) within a wavelength range of 1,200 nm to 1,500 nm.

[0074] Furthermore, the curable composition of the present invention can be preferably used for solid-state imaging devices. More specifically, it can be preferably used as a curable composition for optical filters for solid-state imaging devices, and more preferably as a curable composition for color filters for solid-state imaging devices.

[0075] The solid content concentration of the curable composition of the present invention is preferably 5% to 40% by mass. The lower limit is more preferably 7.5% by mass or higher, and even more preferably 10% by mass or higher. The upper limit is more preferably 35% by mass or lower, and even more preferably 30% by mass or lower.

[0076] Hereinafter, each component contained in the curable composition according to the present invention will be described.

[0077] <Compound (A) in which an indole skeleton is directly linked to an oxime group or a ketoxime group>

[0078] The curable composition according to the present invention comprises a compound (compound (A)) in which an indole skeleton is directly linked to an oxime group or a ketoxime group.

[0079] Since the compound (A) has the above structure, it functions as a polymerization initiator. That is, the compound (A) is a polymerization initiator.

[0080] Furthermore, the compound (A) is preferably a photoradical polymerization initiator, and more preferably a photoradical polymerization initiator that generates radicals by light having a wavelength of 150 nm to 300 nm.

[0081] The wavelength of the light at which the compound (A) generates radicals is preferably 150 nm to 460 nm, 150 nm to 420 nm, more preferably 150 nm to 380 nm, and particularly preferably 150 nm to 300 nm.

[0082] The compound (A) is not particularly limited as long as it has a structure in which an indole skeleton and an oxime group or a ketoximine group are directly linked.

[0083] Among them, the indole ring has a structure represented by the following structural formula. Compound (A) has a structure in which an oxime group or a ketoxime group is connected in at least one of the substitution positions of positions 1 to 7 in the indole ring represented by the following structural formula. The bonding position of the oxime group or the ketoxime group is preferably 2 to 7, and particularly preferably 3. In addition, compound (A) may also have other substituents at the substitution position (bonding position) other than the oxime group or the ketoxime group. As other substituents, alkyl groups, aryl groups, heteroaryl groups, halogen atoms, nitro groups, cyano groups, hydroxyl groups, carboxyl groups, alkoxy groups, aryloxy groups, thiol groups, alkylthio groups, arylthio groups, amino groups, alkylamino groups, arylamino groups, etc.

[0084] [Chemical Formula 3]

[0085]

[0086] Furthermore, the oxime group or ketoxime group is a group represented by the following formula (A1) or the following formula (A2). That is, the oxime group or ketoxime group may be a geometric isomer E body (A1) or a geometric isomer Z body (A2). Furthermore, compound (A) may be a mixture of a compound in which the oxime group or ketoxime group is a geometric isomer E body (A1) and a compound in which the oxime group or ketoxime group is a geometric isomer Z body (A2). In addition, the group represented by formula (A1) or formula (A2) is bonded to any of the substitution positions at positions 1 to 7 in the above structural formula through *.

[0087] [Chemical Formula 4]

[0088]

[0089] In formula (A1) and formula (A2), R1 and R2 each independently represent a monovalent substituent, n represents 0 or 1, and * represents a bonding portion to the indole ring.

[0090] The groups represented by formula (A1) and formula (A2) are oxime groups when n is 0, and are ketoximo groups when n is 1.

[0091] In formula (A1) and formula (A2), R1 is preferably an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group, or a heteroaryloxy group. Among them, R1 is more preferably a linear, branched, or cyclic alkyl or aryl group, further preferably an alkyl group having 1 to 4 carbon atoms (also referred to as "carbon number" or "number of carbon atoms"), and particularly preferably a methyl group.

[0092] The aryl group is preferably an aryl group having 6 to 20 carbon atoms, and more preferably an aryl group having 6 to 12 carbon atoms.

[0093] The heteroaryl group is preferably a heteroaryl group having 4 to 20 carbon atoms, and more preferably a heteroaryl group having 4 to 10 carbon atoms.

[0094] The alkoxy group is preferably an alkoxy group having 1 to 6 carbon atoms, and more preferably an alkoxy group having 1 to 4 carbon atoms.

[0095] The aryloxy group is preferably an aryloxy group having 6 to 20 carbon atoms, and more preferably an aryloxy group having 6 to 12 carbon atoms.

[0096] The heteroaryloxy group is preferably a heteroaryloxy group having 4 to 20 carbon atoms, and more preferably a heteroaryloxy group having 4 to 10 carbon atoms.

[0097] Each group represented by R1 may further have a substituent.

[0098] In formula (A1) and formula (A2), R2 is preferably an alkyl group, an aryl group, or a heteroaryl group. In particular, R2 is more preferably an unsubstituted alkyl group, a substituted alkyl group, or an aryl group, and even more preferably an unsubstituted alkyl group or a substituted alkyl group.

[0099] The alkyl group is preferably an alkyl group having 1 to 30 carbon atoms, and more preferably an alkyl group having 1 to 20 carbon atoms.

[0100] The aryl group is preferably an aryl group having 6 to 30 carbon atoms, and more preferably an aryl group having 6 to 20 carbon atoms.

[0101] The heteroaryloxy group is preferably a heteroaryloxy group having 4 to 20 carbon atoms, and more preferably a heteroaryloxy group having 4 to 10 carbon atoms.

[0102] Each group represented by R2 may further have a substituent. Examples of the substituent include the substituents shown in Group A below.

[0103] -Group A-

[0104] Alkyl, aryl, cyano, alkenyl, alkynyl, -NArAr', -SAr, -COOH, -OH, -O-COR c 、-O-CO-OR c 、-CONR a R b 、-NR a -CO-R b 、-O-CO-NR a R b 、-NR a -CO-OR b 、-NR a -CO-NR a R b 、-SO-R c 、-SO2-R c 、-O-SO2-R c 、-SO2-NR a R b 、-NR a -SO2-R a 、-CO-NR a -COR b 、-CO-NR a -SO2-R b 、-SO2-NR a -CO-R b 、-SO2-NR a -SO2-R c 、-Si(R a ) L (OR b ) m and heterocyclic groups

[0105] wherein Ar and Ar' are independently aryl or heteroaryl, R a and R b Each independently represents a hydrogen atom, an alkyl group, an aryl group or a heteroaryl group, R c represents an alkyl group, an aryl group or a heteroaryl group, L and m each independently represent an integer of 0 to 3, and L+m=3.

[0106] The above-mentioned alkyl groups include linear, branched or cyclic alkyl groups. Examples of linear alkyl groups include methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, decyl, dodecyl, and stearyl groups. Examples of branched alkyl groups include isopropyl, isopentyl, neopentyl, and isopropylethyl groups. Examples of alkyl groups with a cyclic structure include preferably 3 to 8 ring atoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopentamethyl, cyclopentaethyl, and cyclopentapropyl groups. In addition, these alkyl groups may also contain O, S, or NR in the middle. Wherein, R represents a hydrogen atom or an alkyl group. Furthermore, these alkyl groups may also be alkyl groups having substituents, more preferably the substituents shown in Group A.

[0107] R2 in formula (A1) and formula (A2) is preferably a group represented by the following formula (3).

[0108] [Chemical Formula 5]

[0109]

[0110] In formula (3), R 11 represents an alkyl group, wherein I2 is CHR 14 When R 11 It can be a hydrogen atom, R 12 represents a hydrogen atom or an alkyl group, R 13 represents an alkyl group, L1 and L2 each independently represent CHR 14 , O, S or NR 14 , R 14 Each independently represents a hydrogen atom or an alkyl group, R 11 、R 12 、R 13 and R 14 Two or more of them may be linked to each other to form a ring structure, Z represents a single bond or an alkylene group having 1 to 6 carbon atoms, and * represents a linking portion to an oxime group or a ketoximo group.

[0111] From the perspective of sensitivity, R in formula (3) 11 An alkyl group having 1 to 10 carbon atoms is preferred.

[0112] From the perspective of sensitivity, R in formula (3) 12 Preferred is a hydrogen atom.

[0113] From the perspective of sensitivity, R in formula (3) 13 An alkyl group having 1 to 10 carbon atoms is preferred.

[0114] Among them, from the perspective of sensitivity, R 11 and R 13 Preferably, they are bonded to each other to form a ring structure, R 11 and R 13More preferably, they are bonded to each other to form an aliphatic hydrocarbon ring structure.

[0115] From the viewpoint of sensitivity, L1 in formula (3) is preferably O, S or NR 14 , more preferably O or NR.

[0116] From the viewpoint of sensitivity, L2 in formula (3) is preferably CHR 14 .

[0117] From the perspective of sensitivity, the above CHR 14 R in 14 Preferred is a hydrogen atom.

[0118] From the perspective of sensitivity, the above NR 14 R in 14 An alkyl group is preferred, an alkyl group having 1 to 10 carbon atoms is preferred, a methyl group or a cycloalkyl group is more preferred, and a methyl group, a cyclopentyl group or a cyclohexyl group is particularly preferred.

[0119] From the viewpoint of sensitivity, Z in formula (3) is preferably a single bond or an alkylene group having 1 to 4 carbon atoms, more preferably a single bond, a methylene group or an ethylene group, and particularly preferably a single bond.

[0120] From the viewpoint of sensitivity, R2 in formula (A1) and formula (A2) is preferably a group represented by the following formula (4).

[0121] [Chemical Formula 6]

[0122]

[0123] In formula (4), L3 and L4 each independently represent CHR 16 , O, S or NR 16 , at least one of L3 and L4 is CHR 16 , R 16 represents a hydrogen atom or an alkyl group, R 15 Each independently represents a hydrogen atom or an alkyl group, p represents an integer of 1 to 6, and * represents a linking portion to an oxime group or a ketoximo group.

[0124] From the viewpoint of sensitivity, L3 in formula (4) is preferably O, S or NR 16 .

[0125] From the viewpoint of sensitivity, L4 in formula (4) is preferably CHR 16 .

[0126] R in formula (4) 16 The preferred embodiment is the same as R in formula (3) 14 The preferred method is the same.

[0127] From the perspective of sensitivity, R in formula (4) 15 Preferred is a hydrogen atom.

[0128] From the viewpoint of sensitivity, p in formula (4) is preferably an integer of 3 to 5, more preferably 3 or 4, and particularly preferably 3.

[0129] Preferred specific examples of R2 in formula (A1) and formula (A2) are shown below, but the present invention is not limited thereto. In addition, * represents the bonding position to the oxime group or ketoximine group.

[0130] [Chemical Formula 7]

[0131]

[0132] [Chemical Formula 8]

[0133]

[0134] Among them, from the viewpoint of sensitivity, R2 in formula (A1) and formula (A2) is preferably at least one group selected from Y-1, Y-2, Y-5, Y-26 to Y-29, and Y-33 to Y-42.

[0135] From the viewpoint of sensitivity, the compound (A) is preferably a compound represented by the following formula (1).

[0136] [Chemical Formula 9]

[0137]

[0138] In formula (1), R1 represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group or a heteroaryloxy 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 or a monovalent organic group, Ar represents an aryl group or a heteroaryl group, and n represents 0 or 1.

[0139] R1 and R2 in formula (1) have the same preferred embodiments as those of R1 and R2 in formula (A1) and formula (A2), and more preferred embodiments are also the same.

[0140] Examples of the halogen atom in R3 to R7 include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0141] Examples of the monovalent organic groups of R3 to R7 include hydroxyl, amino, alkyl, alkenyl, heterocyclic, aryl, heteroaryl, acyl, nitro, cyano, sulfo, alkylaminocarbonyl, alkoxycarbonyl, alkylthio, arylthio, morpholino, alkoxyalkyl, carboxyl, and carboxyalkyl. Furthermore, these substituents may further have substituents, and the substituents may be bonded to form a ring structure.

[0142] Furthermore, the monovalent organic group preferably has 0 to 100 carbon atoms, more preferably 0 to 50 carbon atoms, and particularly preferably 1 to 12 carbon atoms.

[0143] The aryl group in Ar is preferably an aryl group having 6 to 20 carbon atoms, more preferably an aryl group having 6 to 12 carbon atoms.

[0144] The heteroaryl group in Ar is preferably a heteroaryl group having 4 to 20 carbon atoms, more preferably a heteroaryl group having 4 to 12 carbon atoms.

[0145] Furthermore, these substituents may have further substituents, and the substituents may be bonded to each other to form a ring structure.

[0146] Among them, Ar in formula (1) is preferably a group represented by the following formula (2).

[0147] [Chemical Formula 10]

[0148]

[0149] In formula (2), Ar1 and Ar2 each independently represent an arylene group or a heteroarylene group, and R 21 Each independently represents a halogen atom or a monovalent organic group, m represents an integer of 0 to 5, and * represents a bonding portion to the nitrogen atom of the indole ring.

[0150] Ar1 in formula (2) is preferably an arylene group having 6 to 20 carbon atoms, more preferably an arylene group having 6 to 12 carbon atoms. The arylene group may further have a substituent such as a halogen atom and a monovalent organic group described below. Among them, Ar1 is preferably a phenylene group or a methylphenylene group.

[0151] Furthermore, when Ar1 in formula (2) is a phenylene group or a substituted phenylene group, the bonding position of L1 to the nitrogen atom of the indole ring is preferably the meta position or the para position, more preferably the para position, from the viewpoint of sensitivity.

[0152] Ar2 in formula (2) is preferably an arylene group having 6 to 20 carbon atoms or a heteroarylene group having 4 to 20 carbon atoms, and more preferably an arylene group having 6 to 12 carbon atoms or a heteroarylene group having 4 to 10 carbon atoms.

[0153] As R in formula (2) 21 Examples of the monovalent organic group include hydroxyl, amino, alkyl, cycloalkyl, alkenyl, heterocyclic, aryl, heteroaryl, acyl, nitro, cyano, sulfo, alkylaminocarbonyl, alkoxycarbonyl, alkylthio, arylthio, fusinyl, alkoxyalkyl, carboxyl, and carboxyalkyl. These monovalent organic groups may further have a substituent, and the substituents may be bonded to form a ring structure.

[0154] The molecular weight of the compound (A) is preferably 200 to 2,000, more preferably 300 to 1,000, and even more preferably 400 to 900.

[0155] The compound (A) preferably has absorption at either a wavelength of 248 nm, which is a KrF absorption region, or a wavelength of 365 nm, which is an i-line absorption region, and more preferably has absorption at a wavelength of 248 nm.

[0156] From the viewpoint of sensitivity, the molar absorption coefficient of compound (A) at a wavelength of 248 nm is preferably 5,000 L·mol -1 cm -1 More than 10,000 L·mol -1 cm -1 More than, more preferably 20,000 L·mol -1 cm -1 Above, particularly preferably 30,000 L·mol -1 cm -1 The upper limit of the molar absorption coefficient at a wavelength of 248 nm is not particularly limited, but is 200,000 L·mol -1 cm -1 the following.

[0157] In addition, the long-wavelength absorption end (the longest wavelength with a molar absorption coefficient of less than 100) of compound (A) is preferably 450 nm or less, preferably 400 nm or less, and preferably 380 nm or less. The long-wavelength absorption end is within this region, thereby preventing blurring caused by yellow light and providing excellent photostability during synthesis. Furthermore, compound (A) does not exhibit a yellowish hue, thus providing excellent color reproducibility when used in color filters, etc.

[0158] The molar absorption coefficient of compound (A) was measured by the following method.

[0159] Accurately weigh 12.5 mg of the polymerization initiator into a 100 mL volumetric flask. Add acetonitrile to dissolve completely. Remove 2 mL of the polymerization initiator solution using a quantitative pipette and add water to the mark in a 25 mL volumetric flask. This is used as the measurement sample.

[0160] The sample was added to a 5 mL quartz glass cuvette (1 cm square), and the absorbance was measured in air to calculate the gram absorption coefficient. The measurement instrument used was a UV-visible-near-infrared spectrophotometer UH4150 (manufactured by Hitachi High-Tech Science Corporation).

[0161] Specific examples of the compound (A) are shown below, but it goes without saying that the invention is not limited thereto.

[0162] [Chemical Formula 11]

[0163]

[0164] [Chemical Formula 12]

[0165]

[0166] [Chemical Formula 13]

[0167]

[0168] [Chemical Formula 14]

[0169]

[0170] [Chemical Formula 15]

[0171]

[0172] [Chemical Formula 16]

[0173]

[0174] Specific examples of compound (A) include, in addition to the above-mentioned specific examples, the oxime ester compounds described in International Publication No. 2015 / 152153 (specifically, compounds No. 1 to No. 212), and the compounds described in International Publication No. 2017 / 051680, which have one indole skeleton and two or more oxime groups in the molecule (i.e., in one molecule) (specifically, compounds No. 1 to No. 128).

[0175] Specific examples of the compound (A) include compounds containing two or more indole rings in one molecule.

[0176] Specific examples of the compound (A) include compounds having -N(R a )2、-SR a 、-OR a (R a Each independently represents a hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group. ) or other electron-donating group. These compounds correspond to (A-14), (A-15), (A-16), (A-17), (A-31), (A-32), (A-51), (A-52), (A-53), (A-54), (A-55), (A-56), and (A-57) in the above-mentioned specific examples.

[0177] Further, as the specific example of compound (A), the compound of the structure comprising 3 or more condensed rings different from indole ring in 1 molecule can be enumerated.Wherein, the structure of 3 or more condensed rings is not particularly limited, and is preferably carbazole, dibenzothiophene, dibenzofuran, fluorene etc. In addition, it is a particularly good mode that the structure of 3 or more condensed rings has acyl group.As these compounds, (A-30), (A-34), (A-35), (A-36), (A-37), (A-38), (A-39), (A-40), (A-58), (A-60), (A-61), (A-62), (A-63), (A-64), (A-65), (A-66), (A-67) and (A-68) in the above-mentioned specific example are equivalent.

[0178] The compound (A) may be a compound having two or more oxime groups or ketoximine groups in one molecule, as in the above-mentioned specific examples (A-74) and (A-75).

[0179] In the case of a compound having two or more oxime groups or ketoxime groups in one molecule, one oxime group or ketoxime group needs to be directly linked to the indole skeleton, but the remaining oxime groups or ketoxime groups are not limited thereto.

[0180] The method for producing the compound (A) is not particularly limited, and the compound (A) may be produced by a known method or by referring to a known method.

[0181] Compound (A) can be synthesized, for example, according to or with reference to the method for synthesizing oxime ester compounds described in International Publication No. 2015 / 152153.

[0182] The curable composition according to the present invention may contain one compound (A) alone or two or more. When two or more compounds are used, the total amount thereof is preferably within the following range.

[0183] In the curable composition involved in the present invention, from the viewpoint of being able to improve solvent solubility to obtain a uniform composition, compound (A) is preferably a mixture of two or more compounds. Specifically, compound (A) is preferably a mixture of a compound having one oxime group or ketoxime group in one molecule and a compound having two or more oxime groups or ketoxime groups in one molecule. More specifically, in the case where a compound having one oxime group or ketoxime group in one molecule is set as a monomer (M), a compound having two oxime groups or ketoxime groups is set as a dimer (B), and a compound having three oxime groups or ketoxime groups is set as a trimer (T), compound A can also be a mixture of a monomer (M), a dimer (B) and a trimer (T). When compound (A) is a mixture of a monomer (M), a dimer (B) and a trimer (T), the respective content ratios are preferably 60% to 99.89% by mass of the monomer (M), 0.10% to 30% by mass of the dimer (B), and 0.01% to 10% by mass of the trimer (T). More preferably, the monomer (M) is 80% to 99.49% by mass, the dimer (B) is 0.50% to 10% by mass, and the trimer (T) is 0.01% to 5% by mass. The monomer (M) is 85% to 98.99% by mass, the dimer (B) is 1.00% to 7% by mass, and the trimer (T) is 0.01% to 3% by mass.

[0184] The geometrical isomers (E isomer / Z isomer) of the oxime group or ketoxime group constituting the monomer (M), dimer (B) and trimer (T) are not particularly limited, but generally the E isomer accounts for 50% or more and the Z isomer is less than 50%.

[0185] From the viewpoint of sensitivity, the content of compound (A) is preferably 0.01% by mass to 20% by mass, more preferably 0.05% by mass to 15% by mass, further preferably 0.1% by mass to 10% by mass, and particularly preferably 0.1% by mass to 5% by mass, relative to the total solid content of the curable composition.

[0186] In the curable composition of the present invention, a portion of compound (A) may be hydrolyzed and contained in the form of an oxime. In terms of sensitivity, the amount of hydrolyzed oxime per 100 parts by mass of compound (A) is preferably less than 1 part by mass, and more preferably less than 0.5 parts by mass. While the lower limit of the amount of hydrolyzed oxime is not specified, it is generally 0.001 parts by mass or more per 100 parts by mass of compound (A).

[0187] When a portion of Compound (A) is hydrolyzed, the carboxylic acid that forms the oxime ester is released. In terms of sensitivity, the free carboxylic acid is preferably less than 1 part by mass, and more preferably less than 0.5 parts by mass, per 100 parts by mass of Compound (A). While the lower limit of the free carboxylic acid content is not specified, it is generally 0.001 parts by mass or more per 100 parts by mass of Compound (A).

[0188] <Other radical polymerization initiators>

[0189] The curable composition according to the present invention may contain a radical polymerization initiator other than the compound (A).

[0190] Examples of other radical polymerization initiators include oxime compounds, α-aminoacetophenone compounds, α-hydroxyketone compounds, and acylphosphine compounds.

[0191] Among them, oxime compounds are preferred.

[0192] By using the compound (A) together with other radical polymerization initiators, a pattern having a more excellently balanced rectangularity can be obtained.

[0193] As oxime compounds, the compounds described in paragraph 0142 of International Publication No. 2022 / 085485, the polymers described in Japanese Patent Application Publication No. 2020-172619, the compounds represented by Formula 1 described in International Publication No. 2020 / 152120, the oxime ester compounds described in International Publication No. 2021 / 023144, etc. can be mentioned. As specific examples and commercially available products of oxime compounds, the compounds described in paragraph 0142 of International Publication No. 2022 / 085485 can be used. And, as a commercially available product, TR-PBG-327 (manufactured by TRONLY Corporation) can be mentioned.

[0194] Furthermore, as the oxime compound, a non-coloring compound or a highly transparent compound that is not easily discolored is preferably used. Commercially available products include ADEKA ARKLS NCI-730, NCI-831, and NCI-930 (all manufactured by ADEKA CORPORATION).

[0195] In addition, as other radical polymerization initiators, the fluorenylaminoketone-based photoinitiator described in Japanese Unexamined Patent Application Publication No. 2020-507664, the photopolymerization initiator represented by the general formula (1) in Japanese Unexamined Patent Application Publication No. 2021-173858, the photopolymerization initiator described in paragraphs 0022 to 0024 of Japanese Unexamined Patent Application Publication No. 2021-173858, the photopolymerization initiator represented by the general formula (1) in Japanese Unexamined Patent Application Publication No. 2021-170089, the photopolymerization initiator described in paragraphs 0117 to 0120 of Japanese Unexamined Patent Application Publication No. 2021-170089, Compounds described in Japanese Patent Application Publication No. 2021-181406, photopolymerization initiators described in Japanese Patent Application Publication No. 2022-013379, compounds represented by formula (1) described in Japanese Patent Application Publication No. 2022-015747, fluorine-containing fluorene oxime ester photoinitiators described in Japanese Translation of Patent Table No. 2021-507058, initiators described in the specification of Chinese Patent Application Publication No. 110764367, initiators described in Japanese Translation of Patent Table No. 2022-518535, initiators described in International Publication No. 2021 / 175855, etc.

[0196] Furthermore, as the oxime compound, the compounds described in paragraphs 0143 to 0149 of International Publication No. 2022 / 085485 can be used.

[0197] Specific examples of the oxime compound include the compounds described in paragraphs 0083 to 0105 of Japanese Patent No. 4600600.

[0198] Furthermore, as the oxime compound, the following compounds can be particularly preferably exemplified.

[0199] [Chemical Formula 17]

[0200]

[0201] [Chemical Formula 18]

[0202]

[0203] [Chemical Formula 19]

[0204]

[0205] [Chemical Formula 20]

[0206]

[0207] The curable composition according to the present invention may contain one type of other radical polymerization initiator alone, or may contain two or more types.

[0208] The mass ratio when used simultaneously with other free radical polymerization initiators is not particularly limited. From the viewpoint of degassing inhibition, the content of compound (A) relative to the total mass of the polymerization initiator is preferably 10 mass % or more, more preferably 50 mass % or more, further preferably 80 mass % or more, and particularly preferably 90 mass % or more.

[0209] <Resin (B)>

[0210] The curable composition according to the present invention contains a resin (B).

[0211] For example, a resin is formulated for use in dispersing pigments and the like in a curable composition or as an adhesive. Furthermore, a resin primarily used to disperse pigments and the like in a curable composition is also referred to as a dispersant. However, these uses of the resin are merely examples, and the resin may also be used for purposes other than these.

[0212] In the curable composition of the present invention, the resin (B) includes a resin (B1) having a graft chain and a crosslinkable group. Hereinafter, the resin (B1) having a graft chain and a crosslinkable group is simply referred to as resin (B1).

[0213] [Resin (B1) having a graft chain and a crosslinking group]

[0214] First, the resin (B1) having a graft chain and a crosslinkable group will be described.

[0215] Resin (B1) is a resin having a graft chain and a crosslinking group. Resin (B1) is not particularly limited as long as it has a graft chain and a crosslinking group in the molecule. Resin (B1) is equivalent to a radical curable compound by having a free radical polymerizable group as a crosslinking group.

[0216] The graft chain in the resin (B1) is not particularly limited, but is preferably at least one selected from a polyether chain, a polyester chain, and a poly(meth)acrylic acid chain. The weight average molecular weight of the graft chain is preferably 1,000 or more, more preferably 2,000 or more.

[0217] In the resin (B1), the content of the repeating unit having a graft chain is preferably 0.1 to 50 mol%, more preferably 1 to 30 mol%, and even more preferably 5 to 20 mol%, based on the total repeating units.

[0218] Furthermore, the crosslinkable group is not particularly limited, but is preferably at least one group selected from an ethylenically unsaturated group and a cyclic ether group. From the perspective of degassing inhibition, the crosslinkable group preferably has a (meth)acryloyl group, an epoxy group, or an oxetane group.

[0219] The crosslinking group may be introduced into the graft chain, into a side chain terminal different from the graft chain, or into a main chain terminal. From the viewpoint of dispersibility, it is preferred that the crosslinking group be introduced into a side chain terminal different from the graft chain.

[0220] In resin (B1), the content of repeating units having a crosslinkable group is preferably 5 to 90 mol%, more preferably 10 to 80 mol%, and even more preferably 20 to 70 mol%, based on the total repeating units in resin (A).

[0221] The resin (B1) preferably has at least one group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group, and particularly preferably has a carboxylic acid group.

[0222] These groups are preferably contained in the resin (B1) so as to satisfy the preferred range of the acid value described later.

[0223] From the viewpoint of alkali developability, the resin (B1) is preferably an acrylic resin.

[0224] Here, the term "resin (B1) is an acrylic resin" means a resin having a main chain obtained by polymerizing a (meth)acrylic acid monomer.

[0225] The resin (B1) is preferably an acrylic resin having a poly(meth)acrylic acid chain, a polyester chain, or a polyether chain as a graft chain, a (meth)acryloyl group as a crosslinkable group, and a carboxylic acid group.

[0226] The weight average molecular weight of the resin (B1) is preferably 3,000 to 50,000, more preferably 5,000 to 30,000, and even more preferably 10,000 to 25,000.

[0227] The acid value of the resin (B1) is preferably 30 mgKOH / g to 200 mgKOH / g, more preferably 40 mgKOH / g to 100 mgKOH / g.

[0228] Specific examples of the resin (B1) include C2-1 to C2-6 described in the Examples below.

[0229] Specific examples of the resin (B1) include, for example, the “resin having an oxetane group in a side chain” described in International Publication No. 2021 / 182268, the “dispersant resin having a crosslinkable group, an acid group, and a polyester chain as a graft chain” described in International Publication No. 2018 / 037812, and the “polyester-type dispersant resin having an oxetane group or an unsaturated crosslinkable group in a graft portion” described in Japanese Patent Application Laid-Open No. 2018-101039. "Dispersant resin having a quaternary ammonium salt and a carbon-carbon unsaturated group as a cross-linking group" described in International Publication No. 2020 / 166510, "Polyimide or polyamic acid dispersant resin having a cross-linking group and a graft chain" described in International Publication No. 2022 / 019253, "Dispersant resin having a cross-linking group and a graft chain, and a main chain having both an ester bond and an amide bond" described in International Publication No. 2022 / 019255, etc.

[0230] The curable composition according to the present invention may contain one type of resin (B1) alone, or two or more types thereof.

[0231] The content of the resin (B1) is preferably 5% by mass to 40% by mass, more preferably 10% by mass to 30% by mass, based on the total solid content of the curable composition.

[0232] [Resins other than resin (B1)]

[0233] The curable composition according to the present invention may contain resins other than the resin (B1). Hereinafter, when simply referred to as "resin", it means resins other than the resin (B1).

[0234] As resins other than the resin (B1), resins that are radical curable compounds, that is, resins having radical polymerizable groups can be used.

[0235] In addition, a resin having a radical polymerizable group also corresponds to a radical curable compound.

[0236] Furthermore, the curable composition according to the present invention may further contain a resin other than the radical curable compound.

[0237] The weight average molecular weight of the resin is preferably 3,000 to 2,000,000. The upper limit is preferably 1,000,000 or less, more preferably 500,000 or less. The lower limit is preferably 4,000 or more, more preferably 5,000 or more.

[0238] As resin, can enumerate (methyl) acrylic resin, epoxy resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene ether phosphine oxide resin, polyimide resin, polyamide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, vinyl acetate resin, polyvinyl alcohol resin, polyvinyl acetal resin, polyurethane resin, polyurea resin etc..In these resins, can use 1 kind alone, can also use 2 or more kinds in mixture.As cyclic olefin resin, from the viewpoint of improving heat resistance, preferably norbornene resin.

[0239] Examples of commercially available norbornene resins include the ARTON series manufactured by JSR Corporation (e.g., ARTON F4520). Furthermore, the resins described in Examples of International Publication No. 2016 / 088645, the resins described in Japanese Patent Application Laid-Open No. 2017-057265, the resins described in Japanese Patent Application Laid-Open No. 2017-032685, the resins described in Japanese Patent Application Laid-Open No. 2017-075248, the resins described in Japanese Patent Application Laid-Open No. 2017-066240, the resins described in Japanese Patent Application Laid-Open No. 2017-167513, the resins described in Japanese Patent Application Laid-Open No. 2017-173787, the resins described in Japanese Patent Application Laid-Open No. 2017-206689, and the resins described in Japanese Patent Application Laid-Open No. 2017-066240. The resins described in paragraphs 041 to 0060, the resins described in paragraphs 0022 to 0071 of Japanese Patent Application No. 2018-010856, the blocked polyisocyanate resins described in Japanese Patent Application No. 2016-222891, the resins described in Japanese Patent Application No. 2020-122052, the resins described in Japanese Patent Application No. 2020-111656, the resins described in Japanese Patent Application No. 2020-139021, and the resins described in Japanese Patent Application No. 2017-138503, which contain structural units having a ring structure in the main chain and structural units having biphenyl groups in the side chain. In addition, as the resin, a resin having a fluorene skeleton can also be preferably used. Regarding the resin having a fluorene skeleton, reference can be made to the description of U.S. Patent Application Publication No. 2017 / 0102610, which is incorporated into this specification. Furthermore, as the resin, the resins described in paragraphs 0199 to 0233 of Japanese Patent Application Laid-Open No. 2020-186373, the alkali-soluble resins described in Japanese Patent Application Laid-Open No. 2020-186325, the resin represented by formula (1) described in Korean Patent Application No. 10-2020-0078339, and the copolymer containing an epoxy group and an acid group described in International Publication No. 2022 / 030445 can also be used.

[0240] As the resin, it is preferred to use a resin having an acid group. Examples of the acid group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, and a phenolic hydroxyl group. These acid groups may be one or more. For example, a resin having an acid group can be used as an alkali-soluble resin. The acid value of the resin having an acid group is preferably 30 to 500 mgKOH / g. The lower limit is preferably 50 mgKOH / g or more, more preferably 70 mgKOH / g or more. The upper limit is preferably 400 mgKOH / g or less, more preferably 200 mgKOH / g or less, further preferably 150 mgKOH / g or less, and most preferably 120 mgKOH / g or less.

[0241] As the resin, the compounds described in paragraphs 0056 to 0059 of International Publication No. 2022 / 085485 can also be used.

[0242] As the resin, a resin having a polymerizable group is also preferably used. The polymerizable group may include an ethylenically unsaturated group and a cyclic ether group. Among them, from the viewpoint of degassing inhibition, a resin having a (meth)acryloyl group, an epoxy group or an oxetane group is preferably used.

[0243] Furthermore, as the resin, a resin (hereinafter also referred to as resin Ep) having at least one repeating unit selected from the repeating unit represented by formula (Ep-1) and the repeating unit represented by formula (Ep-2) (hereinafter also referred to as repeating unit Ep) can also be used. The above-mentioned resin Ep may contain only one of the repeating unit represented by formula (Ep-1) and the repeating unit represented by formula (Ep-2), or may contain the repeating unit represented by formula (Ep-1) and the repeating unit represented by formula (Ep-2) separately. When containing these two repeating units, the ratio of the repeating unit represented by formula (Ep-1) to the repeating unit represented by formula (Ep-2) is preferably a repeating unit represented by formula (Ep-1):repeating unit represented by formula (Ep-2) = 5:95 to 95:5, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20 in terms of molar ratio.

[0244] [Chemical Formula 21]

[0245]

[0246] In formula (Ep-1) and (Ep-2), L 1 represents a single bond or a divalent linking group, R 1 represents a hydrogen atom or a substituent. 1 The substituent represented by may be an alkyl group or an aryl group, preferably an alkyl group. The number of carbon atoms in the alkyl group is preferably 1 to 10, more preferably 1 to 5, and even more preferably 1 to 3. 1 Preferably, L is a hydrogen atom or a methyl group.1 Examples of the divalent linking group include alkylene groups (preferably those having 1 to 12 carbon atoms), arylene groups (preferably those having 6 to 20 carbon atoms), -NH-, -SO-, -SO2-, -CO-, -O-, -COO-, -OCO-, -S-, and combinations of two or more of these. The alkylene group may be linear, branched, or cyclic, preferably linear or branched. Furthermore, the alkylene group may or may not be substituted. Examples of the substituent include hydroxyl groups and alkoxy groups.

[0247] The content of the repeating unit Ep in the resin Ep is preferably 1 to 100 mol% based on all the repeating units of the resin Ep. The upper limit is more preferably 90 mol% or less, and even more preferably 80 mol% or less. The lower limit is more preferably 2 mol% or more, and even more preferably 3 mol% or more.

[0248] The resin Ep may contain other repeating units in addition to the above-mentioned repeating unit Ep. Examples of the other repeating units include repeating units having an acid group and repeating units having an ethylenically unsaturated group.

[0249] Examples of the acid group include a phenolic hydroxyl group, a carboxyl group, a sulfo group, and a phosphoric acid group. A phenolic hydroxyl group or a carboxyl group is preferred, and a carboxyl group is more preferred.

[0250] Examples of the ethylenically unsaturated group include a vinyl group, a styryl group, a (meth)allyl group, and a (meth)acryloyl group.

[0251] When the resin Ep contains repeating units having an acid group, the content of the repeating units having an acid group in the resin Ep is preferably 5 mol% to 85 mol% based on all the repeating units in the resin Ep. The upper limit is more preferably 60 mol% or less, and even more preferably 40 mol% or less. The lower limit is more preferably 8 mol% or more, and even more preferably 10 mol% or more.

[0252] When the resin Ep contains repeating units having an ethylenically unsaturated group, the content of the repeating units having an ethylenically unsaturated group in the resin Ep is preferably 1 to 65 mol% based on all the repeating units in the resin Ep. The upper limit is more preferably 45 mol% or less, and even more preferably 30 mol% or less. The lower limit is more preferably 2 mol% or more, and even more preferably 3 mol% or more.

[0253] Resin Ep preferably further includes repeating units having an aromatic hydrocarbon ring. As the aromatic hydrocarbon ring, a benzene ring or a naphthalene ring is preferred, preferably a benzene ring. The aromatic hydrocarbon ring may have a substituent. As a substituent, an alkyl group or the like can be mentioned. In the case where the resin having a cyclic ether group includes a repeating unit having an aromatic hydrocarbon ring, the content of the repeating unit having an aromatic hydrocarbon ring is preferably 1 mol% to 65 mol% in all repeating units of the resin having a cyclic ether group. The upper limit is more preferably 45 mol% or less, and more preferably 30 mol% or less. The lower limit is more preferably 2 mol% or more, and more preferably 3 mol% or more. As repeating units having an aromatic hydrocarbon ring, repeating units derived from monofunctional polymerizable compounds having an aromatic hydrocarbon ring such as vinyltoluene and benzyl (meth)acrylate can be mentioned.

[0254] As the resin, a resin containing a repeating unit derived from a compound represented by the following formula (X) is also preferably used.

[0255] [Chemical Formula 22]

[0256]

[0257] In formula (X), R 1 represents a hydrogen atom or a methyl group, R 21 and R 22 Each independently represents an alkylene group, and n represents an integer of 0 to 15. 21 and R 22 The number of carbon atoms in the alkylene group is preferably 1 to 10, more preferably 1 to 5, further preferably 1 to 3, and particularly preferably 2 or 3. n represents an integer of 0 to 15, preferably an integer of 0 to 5, more preferably an integer of 0 to 4, and further preferably an integer of 0 to 3.

[0258] Examples of the compound represented by formula (X) include ethylene oxide- or propylene oxide-modified (meth)acrylates of para-cumylphenol, and commercially available products include ARONIX M-110 (manufactured by TOAGOSEI CO., LTD.).

[0259] As the resin, a resin having an aromatic carboxyl group (hereinafter also referred to as resin Ac) is also preferably used. In resin Ac, the aromatic carboxyl group may be contained in the main chain of the repeating unit or in the side chain of the repeating unit. The aromatic carboxyl group is preferably contained in the main chain of the repeating unit. In addition, in this specification, the aromatic carboxyl group refers to a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring. Among the aromatic carboxyl groups, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, more preferably 1 to 2.

[0260] The resin Ac is preferably a resin containing at least one repeating unit selected from the group consisting of a repeating unit represented by the following formula (Ac-1) and a repeating unit represented by the following formula (Ac-2).

[0261] [Chemical Formula 23]

[0262]

[0263] In formula (Ac-1), Ar 1 represents a group containing an aromatic carboxyl group, L 1 Indicates -COO- or CONH-, L 2 represents a divalent linking group.

[0264] In formula (Ac-2), Ar 10 represents a group containing an aromatic carboxyl group, L 11 Indicates -COO- or CONH-, L 12 represents a trivalent connecting group, P 10 represents a polymer chain.

[0265] In formula (Ac-1), as Ar 1 Examples of the aromatic carboxyl group-containing group include structures derived from aromatic tricarboxylic anhydride and structures derived from aromatic tetracarboxylic anhydride. Examples of the aromatic tricarboxylic anhydride and aromatic tetracarboxylic anhydride include compounds of the following structures.

[0266] [Chemical Formula 24]

[0267]

[0268] In the above formula, Q 1 It represents a single bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the following formula (Q-1), or a group represented by the following formula (Q-2).

[0269] [Chemical Formula 25]

[0270]

[0271] Ar 1 The group containing an aromatic carboxyl group represented by the formula (I) may have a polymerizable group. The polymerizable group is preferably an ethylenically unsaturated group or a cyclic ether group, and more preferably an ethylenically unsaturated group.

[0272] As Ar 1 Specific examples of the aromatic carboxyl group-containing group include a group represented by the following formula (Ar-11), a group represented by the following formula (Ar-12), and a group represented by the following formula (Ar-13).

[0273] [Chemical Formula 26]

[0274]

[0275] In the formula (Ar-11), n1 represents an integer of 1 to 4, preferably 1 or 2, and more preferably 2.

[0276] In formula (Ar-12), n2 represents an integer of 1 to 8, preferably an integer of 1 to 4, more preferably 1 or 2, and even more preferably 2.

[0277] In formula (Ar-13), n3 and n4 each independently represent an integer of 0 to 4, preferably an integer of 0 to 2, more preferably 1 or 2, and further preferably 1. However, at least one of n3 and n4 is an integer of 1 or greater.

[0278] In formula (Ar-13), Q 1 It represents a single bond, -O-, -CO-, -COOCH2CH2OCO-, -SO2-, -C(CF3)2-, a group represented by the above formula (Q-1), or a group represented by the above formula (Q-2).

[0279] In the formulas (Ar-11) to (Ar-13), *1 represents 1 bonding position.

[0280] In formula (Ac-1), L 1 represents -COO- or CONH-, preferably represents -COO-.

[0281] As L in formula (Ac-1) 2 The divalent linking group represented by alkylene, arylene, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and a group formed by combining two or more of these. The number of carbon atoms of the alkylene is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The alkylene group may be any of linear, branched, and cyclic. The number of carbon atoms of the arylene group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The alkylene and arylene groups may have substituents. Examples of the substituents include hydroxyl groups and the like. L 2 The divalent linking group represented by is preferably -L 2a -O- represented by the group. 2aExamples include: alkylene groups; arylene groups; groups formed by combining an alkylene group and an arylene group; and groups formed by combining at least one selected from an alkylene group and an arylene group with at least one selected from -O-, -CO-, -COO-, -OCO-, -NH-, and -S-. Alkylene groups are preferred. The alkylene group preferably has 1 to 30 carbon atoms, more preferably 1 to 20, and even more preferably 1 to 15. The alkylene group may be linear, branched, or cyclic. The alkylene and arylene groups may have substituents. Examples of substituents include hydroxyl groups.

[0282] As Ar in formula (Ac-2) 10 The group containing an aromatic carboxyl group represented by 1 The meanings and preferences are the same.

[0283] In formula (Ac-2), L 11 represents -COO- or CONH-, preferably represents -COO-.

[0284] As in formula (Ac-2) L12 The trivalent linking group represented by the present invention includes hydrocarbon groups, -O-, -CO-, -COO-, -OCO-, -NH-, -S-, and groups formed by combining two or more of these. Examples of the hydrocarbon group include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The number of carbon atoms in the aliphatic hydrocarbon group is preferably 1 to 30, more preferably 1 to 20, and even more preferably 1 to 15. The aliphatic hydrocarbon group may be any of linear, branched, and cyclic. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 30, more preferably 6 to 20, and even more preferably 6 to 10. The hydrocarbon group may have a substituent. Examples of the substituent include hydroxyl groups and the like. L 12 The trivalent linking group represented is preferably a group represented by the following formula (L12-1), and more preferably a group represented by the following formula (L12-2).

[0285] [Chemical Formula 27]

[0286]

[0287] In formula (L12-1), L 12b represents a trivalent connecting group, X 1 represents S, *1 represents L in formula (Ac-2) 11 The bonding position of *2 indicates the bonding position with P of formula (Ac-2) 10 The bonding position of L 12b Examples of the trivalent linking group include a hydrocarbon group and a group consisting of a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. Preferably, it is a hydrocarbon group or a group consisting of a hydrocarbon group and -O-.

[0288] In formula (L12-2), L 12c represents a trivalent connecting group, X 1 represents S, *1 represents L in formula (Ac-2) 11 The bonding position of *2 indicates the bonding position with P of formula (Ac-2) 10 The bonding position of L 12c Examples of the trivalent linking group represented by include a hydrocarbon group and a group consisting of a hydrocarbon group and at least one selected from -O-, -CO-, -COO-, -OCO-, -NH- and -S-. A hydrocarbon group is preferred.

[0289] In formula (Ac-2), P 10 Represents a polymer chain. 10 The polymer chain represented preferably has at least one repeating unit selected from the group consisting of poly(meth)acrylic acid repeating units, polyether repeating units, polyester repeating units, and polyol repeating units. 10 The weight average molecular weight is preferably 500 to 20,000. The lower limit is more preferably 1,000 or more. The upper limit is more preferably 10,000 or less, further preferably 5,000 or less, and particularly preferably 3,000 or less. 10 When the weight average molecular weight is within the above range, the pigment has good dispersibility in the composition. When the resin having an aromatic carboxyl group is a resin having a repeating unit represented by formula (Ac-2), the resin is preferably used as a dispersant.

[0290] P 10 The polymer chain represented may contain a polymerizable group. Examples of the polymerizable group include ethylenically unsaturated groups.

[0291] The curable composition involved in the present invention preferably contains a resin as a dispersant. Examples of the dispersant include acidic dispersants (acidic resins) and alkaline dispersants (alkaline resins). Here, the acidic dispersant (acidic resin) refers to a resin in which the amount of acid groups is greater than the amount of base groups. As the acidic dispersant (acidic resin), when the total amount of the amount of acid groups and the amount of base groups is set to 100 mol%, the resin in which the amount of acid groups is 70 mol% or more is preferred. The acid group possessed by the acidic dispersant (acidic resin) is preferably a carboxyl group. The acid value of the acidic dispersant (acidic resin) is preferably 10 mgKOH / g to 105 mgKOH / g. In addition, the alkaline dispersant (alkaline resin) refers to a resin in which the amount of base groups is greater than the amount of acid groups. As the alkaline dispersant (alkaline resin), when the total amount of the amount of acid groups and the amount of base groups is set to 100 mol%, the resin in which the amount of base groups is greater than 50 mol%.

[0292] The basic group contained in the basic dispersant is preferably an amino group.

[0293] The resin used as the dispersant is preferably a resin having a graft chain other than the resin (B1) described above. Detailed information on the resin having a graft chain, i.e., the graft polymer, can be found in paragraphs 0025 to 0094 of JP-A-2012-255128, which is incorporated herein by reference.

[0294] Furthermore, from the viewpoint of dispersion stability, the resin is a resin having a graft chain, the graft chain includes at least one selected from a polyether chain, a polyester chain, and a polyacrylic acid chain, and the weight average molecular weight of the graft chain is preferably 1,000 or more.

[0295] The resin used as a dispersant is also preferably a polyimine-based dispersant containing nitrogen atoms in at least one of the main chain and side chains. Polyimine-based dispersants are preferably resins having a main chain and side chains, with at least one of the main chain and side chains containing a basic nitrogen atom, the main chain containing a partial structure having a functional group with a pKa of 14 or less, and the side chains containing 40 to 10,000 atoms. The basic nitrogen atom is not particularly limited as long as it is basic. For information on polyimine-based dispersants, reference may be made to paragraphs 0102 to 0166 of Japanese Patent Application Laid-Open No. 2012-255128, which is incorporated herein by reference.

[0296] The resin used as a dispersant is also 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 polymers). Specific examples of dendrimers include polymer compounds C-1 to C-31 described in paragraphs 0196 to 0209 of JP-A-2013-043962.

[0297] The resin used as a dispersant is also preferably a resin containing repeating units having ethylenically unsaturated groups in their side chains. The content of repeating units having ethylenically unsaturated groups in their side chains is preferably 10 mol% or more, more preferably 10 to 80 mol%, and even more preferably 20 to 70 mol%, based on all repeating units in the resin.

[0298] Furthermore, the resin used as the dispersant is preferably a resin containing an oxetane group in a side chain other than the resin (B1), and more preferably a resin containing a repeating unit having an oxetane group in a side chain.

[0299] The content of repeating units having an oxetane group in the side chain in the resin is preferably 10 mol% or more, more preferably 10 mol% to 80 mol%, and even more preferably 20 mol% to 70 mol% based on all repeating units in the resin.

[0300] In addition, as a dispersant, the resin described in Japanese Patent Application Laid-Open No. 2018-087939, the block copolymers (EB-1) to (EB-9) described in paragraphs 0219 to 0221 of Japanese Patent Application No. 6432077, the polyethyleneimine having a polyester side chain described in International Publication No. 2016 / 104803, the block copolymer described in International Publication No. 2019 / 125940, the block polymer having an acrylamide structural unit described in Japanese Patent Application Laid-Open No. 2020-066687, the block polymer having an acrylamide structural unit described in Japanese Patent Application Laid-Open No. 2020-066688, the dispersant described in International Publication No. 2016 / 104803, etc. can also be used.

[0301] As the dispersant, polyamic acid type dispersion resin or polyimide type dispersion resin can also be used. As these resins, the dispersants described in International Publication No. 2022 / 019253, International Publication No. 2022 / 019254, and International Publication No. 2022 / 019255 can also be used.

[0302] The dispersant can be obtained from commercially available products, and specific examples thereof include the Disperbyk series manufactured by BYK Chemie (e.g., Disperbyk-111, 161, 2001, etc.), the SOLSPERSE series manufactured by Lubrizol Japan Ltd. (e.g., SOLSPERSE 20000, 76500, etc.), and the Ajispar series manufactured by Ajinomoto Fine-Techno Co., Inc. Furthermore, the products described in paragraph 0129 of JP-A-2012-137564 and the products described in paragraph 0235 of JP-A-2017-194662 can also be used as the dispersant.

[0303] When the curable composition of the present invention contains a resin as a radical curable compound, the content of the resin is preferably 1% to 70% by mass relative to the total solid content of the curable composition. The lower limit is more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is more preferably 65% ​​by mass or less, further preferably 60% by mass or less.

[0304] The content of the acid group-containing resin is preferably 1% to 70% by mass relative to the total solids content of the curable composition. The lower limit is more preferably 2% by mass or greater, further preferably 3% by mass or greater, and particularly preferably 5% by mass or greater. The upper limit is more preferably 65% ​​by mass or less, further preferably 60% by mass or less.

[0305] Furthermore, the content of the alkali-soluble resin is preferably 1% to 70% by mass relative to the total solids content of the curable composition. The lower limit is more preferably 2% by mass or more, further preferably 3% by mass or more, and particularly preferably 5% by mass or more. The upper limit is more preferably 65% ​​by mass or less, further preferably 60% by mass or less.

[0306] When the curable composition of the present invention contains a resin as a dispersant, the content of the resin as a dispersant is preferably 0.1% to 30% by mass relative to the total solid content of the curable composition. The upper limit is more preferably 25% by mass or less, and more preferably 20% by mass or less. The lower limit is more preferably 0.5% by mass or more, and more preferably 1% by mass or more. In addition, the content of the resin as a dispersant is preferably 1 to 100 parts by mass relative to 100 parts by mass of the colorant. The upper limit is more preferably 80 parts by mass or less, more preferably 70 parts by mass or less, and particularly preferably 60 parts by mass or less. The lower limit is more preferably 5 parts by mass or more, more preferably 10 parts by mass or more, and particularly preferably 20 parts by mass or more.

[0307] The curable composition according to the present invention may contain only one resin or two or more resins. When containing two or more resins, the total amount of these resins is preferably within the above range.

[0308] <Radical Curable Compound (C)>

[0309] The curable composition according to the present invention contains a radical-curable compound (C).

[0310] Examples of the radical curable compound include compounds having an ethylenically unsaturated group.

[0311] Examples of resin-type radical-curable compounds include the resins described above that contain repeating units having radical polymerizable groups. The weight-average molecular weight (Mw) of the resin-type polymerizable compound is preferably 3,000 to 2,000,000. The upper limit of the weight-average molecular weight is more preferably 1,000,000 or less, and even more preferably 500,000 or less. The lower limit of the weight-average molecular weight is more preferably 3,000 or more, and even more preferably 5,000 or more.

[0312] As the radical curable compound, a radical curable compound (C1) having a molecular weight of less than 3000 can be used. Hereinafter, the radical curable compound (C1) having a molecular weight of less than 3000 is simply referred to as a curable compound (C1).

[0313] Examples of the radical-curable compound (C1) having a molecular weight of less than 3,000 include monomer-type radical-curable compounds, that is, monomers having a radical polymerizable group (hereinafter also referred to as "polymerizable monomers").

[0314] The molecular weight of the monomeric radical curable compound (eg, polymerizable monomer) is less than 3,000, preferably 2,000 or less, more preferably 1,500 or less. The lower limit of the molecular weight of the polymerizable monomer is preferably 100 or more, more preferably 200 or more.

[0315] The compound having an ethylenically unsaturated group as a polymerizable monomer is preferably a tri- to penta-functional (meth)acrylate compound, and more preferably a tri- to hexa-functional (meth)acrylate compound. Specific examples include the compounds described in paragraph 0128 of International Publication No. 2022 / 085485 and the compounds described in Japanese Patent Application Laid-Open No. 2017-194662, the contents of which are incorporated herein.

[0316] As compounds having an ethylenically unsaturated group, compounds described in paragraphs 0129 to 0137 of International Publication No. 2022 / 085485 can also be used. The compound having an ethylenically unsaturated group may be a compound having an acid group such as a carboxyl group, a sulfo group, or a phosphoric acid group, a compound having a caprolactone structure, a compound having an alkyleneoxy group, or a compound having a fluorene skeleton.

[0317] As the compound having an ethylenically unsaturated group, 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 (all manufactured by Taisei Fine Chemical Co., Ltd.), LIGHT ACRYLATE POB-A0 (manufactured by KYOEISHA CHEMICAL Co., Ltd.), and the like are also preferably used.

[0318] In the curable composition according to the present invention, the radical curable compound (C) may be used alone or in combination of two or more. When two or more radical curable compounds are used, the total amount thereof is preferably within the above range.

[0319] The content of the radical curable compound (C) is preferably 0.1% to 50% by mass relative to the total solid content of the curable composition. The lower limit is more preferably 0.5% by mass or more, and even more preferably 1% by mass or more. The upper limit is more preferably 45% by mass or less, and even more preferably 40% by mass or less.

[0320] In the curable composition of the present invention, from the viewpoint of degassing suppression and coating unevenness suppression, the content of the radical curable compound (C1) having a molecular weight of less than 3000 in the radical curable compound (C) is preferably less than 15% by mass, more preferably 14% by mass or less, further preferably 13% by mass or less, and particularly preferably 12% by mass or less, relative to the total solid content of the curable composition. Furthermore, the content of the radical curable compound (e.g., polymerizable monomer) having a molecular weight of less than 3000 may be zero (0), but is preferably 1% by mass or more, more preferably 3% by mass or more, relative to the total solid content of the curable composition.

[0321] Furthermore, in the curable composition of the present invention, from the viewpoint of forming an excellent rectangular pattern, when the mass of the radical curable compound (C1) having a molecular weight of less than 3000 is defined as W1 and the mass of the compound (A) is defined as W2, it is preferred that W1 / W2 < 5, more preferably W1 / W2 < 4, and even more preferably W1 / W2 < 3. Furthermore, it is preferred that 0.1 ≤ W1 / W2, and more preferably 0.5 ≤ W1 / W2.

[0322] <Colorant (D)>

[0323] The curable composition according to the present invention preferably contains a colorant (D).

[0324] Examples of colorants include chromatic colorants and black colorants. Examples of chromatic colorants include those having a maximum absorption wavelength within the wavelength range of 400 nm to 700 nm. Examples include green colorants, red colorants, yellow colorants, violet colorants, blue colorants, and orange colorants.

[0325] The colorant can be a pigment or a dye.

[0326] Furthermore, as the colorant, from the viewpoint of coloring properties and dispersibility, it is preferably at least one pigment selected from the group consisting of diketopyrrolopyrrole pigments, quinacridone pigments, anthraquinone pigments, perylene pigments, phthalocyanine pigments, isoindoline pigments, quinophthalone pigments, azo pigments, azomethine pigments, and dioxazine pigments, and more preferably at least one pigment selected from the group consisting of diketopyrrolopyrrole pigments, phthalocyanine pigments, and isoindoline pigments.

[0327] Furthermore, a black pigment can be used. As the black pigment, carbon black or a pigment containing a titanium atom or a zirconium atom can be used.

[0328] The average primary particle size of the pigment is preferably 1 nm to 200 nm. The lower limit is more preferably 5 nm or more, and further preferably 10 nm or more. The upper limit is more preferably 180 nm or less, further preferably 150 nm or less, and particularly preferably 100 nm or less. In addition, in this specification, the primary particle size of the pigment can be obtained by observing the primary particles of the pigment through a transmission electron microscope and based on the image photograph obtained. Specifically, the projected area of ​​the primary particles of the pigment is obtained, and the equivalent circle diameter corresponding thereto is calculated as the primary particle size of the pigment. In addition, the average primary particle size in this specification is set as the arithmetic mean of the primary particle sizes of 400 primary particles of the pigment. In addition, the primary particles of the pigment refer to independent particles that are not agglomerated.

[0329] The crystallite size determined from the half-value width of a peak originating from any crystal plane in an X-ray diffraction spectrum obtained when CuKα rays of the pigment are used as the X-ray source is preferably 0.1 nm to 100 nm, more preferably 0.5 nm to 50 nm, further preferably 1 nm to 30 nm, and particularly preferably 5 nm to 25 nm.

[0330] As green colorants, phthalocyanine compounds and squaric acid compounds can be mentioned, preferably phthalocyanine compounds. In addition, it is preferred that the green colorant is a pigment. As specific examples of green colorants, green pigments such as CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, 64, 65, and 66 can be mentioned. In addition, as green colorants, compounds described in paragraphs 0143 to 0149 of International Publication No. 2022 / 085485, aluminum phthalocyanine compounds described in Japanese Patent Application Laid-Open No. 2020-070426, diarylmethane compounds described in Japanese Patent Application Laid-Open No. 2020-504758, and green pigments described in the Journal of Color Materials Association, Vol. 95, No. 4, pp. 80 to 84 can also be used.

[0331] The green colorant is preferably CI Pigment Green 7, 36, 58, 59, 62, or 63, and more preferably CI Pigment Green 7, 36, 58, or 59.

[0332] Examples of red colorants include diketopyrrolopyrrole compounds, anthraquinone compounds, azo compounds, naphthol compounds, azomethine compounds, oxadiazole compounds, quinacridone compounds, perylene compounds, and thioindigo compounds. Preferred are diketopyrrolopyrrole compounds, anthraquinone compounds, and azo compounds, and more preferred are diketopyrrolopyrrole compounds. Furthermore, the red colorant is preferably a pigment. Specific examples of red colorants include CI (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, 1 46, 149, 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, etc. As a red colorant, the compounds described in paragraph 0034 of International Publication No. 2022 / 085485 can also be used. As a red colorant, Lumogen F Orange 240 (manufactured by BASF, a red pigment, a perylene pigment) can also be used.

[0333] The red colorant is preferably CI Pigment Red 122, 177, 179, 254, 255, 264, 269, 272, or 291, and more preferably CI Pigment Red 177, 254, 264, 272, or 291.

[0334] Examples of yellow colorants include azo compounds, azomethine compounds, isoindoline compounds, pteridine compounds, quinophthalone compounds, and perylene compounds. The yellow colorant is preferably a pigment, more preferably an azo pigment, azomethine pigment, isoindoline pigment, pteridine pigment, quinophthalone pigment, or perylene pigment, and even more preferably an azo pigment or azomethine pigment. Specific examples of yellow colorants include CI 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 0, 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 other yellow pigments.

[0335] Furthermore, as a yellow colorant, a nickel azobarbiturate complex having the following structure can also be used.

[0336] [Chemical Formula 28]

[0337]

[0338] Furthermore, as yellow colorants, compounds described in paragraphs 0031 to 0033 of International Publication No. 2022 / 085485 can also be used.

[0339] The yellow colorant is preferably CI Pigment Yellow 117, 129, 138, 139, 150, 185, 215, and more preferably CI Pigment Yellow 129, 138, 139, 150, 185, 215.

[0340] Examples of the orange colorant include CI 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.

[0341] Examples of the violet colorant include violet pigments such as CI Pigment Violet 1, 19, 23, 27, 32, 37, 42, 60, and 61.

[0342] Examples of blue colorants include CI 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 containing phosphorus atoms can also be used as blue colorants. Specific examples include the compounds described in paragraphs 0022 to 0030 of JP-A-2012-247591 and paragraph 0047 of JP-A-2011-157478.

[0343] Dyes can also be used as color colorants. There are no particular limitations on the dyes, and known dyes can be used. For example, dyes such as pyrazole azo, anilino azo, triarylmethane, anthraquinone, anthrapyridone, benzylidene, oxonol, pyrazolotriazole azo, pyridone azo, cyanine, phenothiazine, pyrrolopyrazole azomethine, guanidine, phthalocyanine, benzopyran, indigo, and pyrromethene can be used.

[0344] Pigment multimers can also be used as color colorants. The pigment multimers are preferably dyes used by dissolving in an organic solvent. In addition, the pigment multimers can form particles. When the pigment multimers are particles, they are usually used in a state dispersed in a solvent. Pigment multimers in a particle state can be obtained, for example, by emulsion polymerization, and the compounds and production methods described in Japanese Patent Application Publication No. 2015-214682 can be cited as specific examples. Pigment multimers can also use the compounds described in paragraph 0048 of International Publication No. 2022 / 085485.

[0345] Color colorants can use diarylmethane compounds described in Japanese Patent Application Publication No. 2020-504758, triarylmethane dye polymers described in Korean Patent Application Publication No. 10-2020-0028160, phthalocyanine compounds described in Japanese Patent Application Publication No. 2020-117638, phthalocyanine compounds described in International Publication No. 2020 / 174991, indoline compounds described in Japanese Patent Application Publication No. 2020-160279, or derivatives thereof. salts, compounds represented by formula (1) described in Korean Patent Publication No. 10-2020-0069442, compounds represented by formula (1) described in Korean Patent Publication No. 10-2020-0069730, compounds represented by formula (1) described in Korean Patent Publication No. 10-2020-0069070, compounds represented by formula (1) described in Korean Patent Publication No. 10-2020-0069067, The compound represented by formula (1) described in Patent Publication No. 10-2020-0069062, the zinc phthalocyanine halogenide pigment described in Japanese Patent No. 6809649, the isoindoline compound described in Japanese Patent Publication No. 2020-180176, the phenothiazine compound described in Japanese Patent Publication No. 2021-187913, the quinophthalone compound represented by formula (1) described in Korean Patent Publication No. 10-2020-0030759, the The polymer dyes described in the Publication of Patent No. 10-2020-0061793, the colorants described in the Publication of Japanese Patent No. 2022-029701, the isoindoline compounds described in International Publication No. 2022 / 014635, the aluminum phthalocyanine compounds described in International Publication No. 2022 / 024926, the compounds described in Japanese Patent No. 2022-045895, and the compounds described in International Publication No. 2022 / 050051. The color colorant may be a rotaxane, and the pigment skeleton may be used for the cyclic structure of the rotaxane, the rod-shaped structure, or both structures.

[0346] Two or more chromatic colorants may be used in combination. Furthermore, when two or more chromatic colorants are used in combination, black can be formed by the combination of two or more chromatic colorants.

[0347] As a black colorant, there is no particular limitation, and known black colorants can be used. For example, as inorganic black colorants, carbon black, titanium black, zirconium oxynitride, graphite, etc. can be mentioned, preferably carbon black, titanium black or zirconium oxynitride, more preferably titanium black or zirconium oxynitride. Titanium black refers to black particles containing titanium atoms, preferably low-order titanium oxide, titanium oxynitride. Titanium black can be surface-modified as needed for the purpose of improving dispersibility, suppressing cohesion, etc. For example, the surface of titanium black can be coated with silicon oxide, titanium oxide, germanium oxide, aluminum oxide, magnesium oxide or zirconium oxide. In addition, it is also possible to perform treatment using a water-repellent substance as shown in Japanese Patent Application Laid-Open No. 2007-302836. As a black colorant, color index (CI) pigment black 1, 7 can also be used. Regarding titanium black, it is preferred that the primary particle size and average primary particle size of each particle are small. Specifically, the average primary particle size is preferably 10 to 45 nm. Titanium black can also be used as a dispersed material. For example, a dispersion containing titanium black particles and silica particles and adjusting the ratio of Si atoms to Ti atoms in the dispersion to be within the range of 0.20 to 0.50 can be cited. Regarding the above-mentioned dispersion, reference can be made to the description of paragraphs 0020 to 0105 of Japanese Patent Application Publication No. 2012-169556, which is incorporated into this specification. Examples of commercially available titanium blacks include titanium black 10S, 12S, 13R, 13M, 13M-C, 13R-N, and 13M-T (product name: manufactured by Mitsubishi Materials Corporation) and Tilack D (product name: manufactured by Ako Kasei Co., Ltd.). As organic black colorants, bisbenzofuranone compounds, azomethine compounds, perylene compounds, and azo compounds can be cited, preferably bisbenzofuranone compounds and perylene compounds. As the bisbenzofuranone compound, compounds described in JP-A-2010-534726, JP-A-2012-515233, JP-A-2012-515234, International Publication No. 2014 / 208348, JP-A-2015-525260, etc. can be mentioned, and for example, they can be obtained as "Irgaphor Black" manufactured by BASF. As the perylene compound, CI Pigment Black 31 and 32 can be mentioned. As the azomethine compound, compounds described in JP-A-01-170601 and JP-A-02-034664 can be mentioned, and for example, they can be obtained as "CHROMO FINE BLACK A1103" manufactured by Dainichiseika Color & Chemicals Mfg. Co., Ltd.Furthermore, as an organic black colorant, perylene black (Lumogen Black FK4280, etc.) and Paliogen Black S0084 described in paragraphs 0016 to 0020 of JP-A-2017-226821 may also be used.

[0348] The curable composition according to the present invention may contain one colorant alone or two or more. When two or more colorants are used, the total amount thereof is preferably within the following range.

[0349] From the perspective of further exerting the effects of the present invention, the content of the colorant is preferably 10% to 75% by mass relative to the total solid content of the curable composition. The upper limit is more preferably 70% by mass or less, and even more preferably 65% ​​by mass or less. The lower limit is more preferably 20% by mass or more, even more preferably 30% by mass or more, and particularly preferably 60% by mass or more.

[0350] <Solvent>

[0351] The curable composition of the present invention preferably contains a solvent. Examples of the solvent include organic solvents. The type of solvent is not particularly limited as long as it satisfies the solubility of the components and the coating properties of the composition. Examples of organic solvents include ester solvents, ketone solvents, alcohol solvents, amide solvents, ether solvents, hydrocarbon solvents, and the like. For details of these, reference can be made to paragraph 0223 of International Publication No. 2015 / 166779, which is incorporated herein by reference. Furthermore, ester solvents substituted with a cyclic alkyl group and ketone solvents substituted with a cyclic alkyl group can also be preferably used. Specific examples of the organic solvent include polyethylene glycol monomethyl ether, dichloromethane, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, ethyl celulose 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, Propylene glycol monomethyl ether acetate, 3-methoxy-N,N-dimethylpropionamide, 3-butoxy-N,N-dimethylpropionamide, propylene glycol diacetate, 3-methoxybutanol, methyl ethyl ketone, γ-butyrolactone, sulfolane, anisole, 1,4-diacetoxybutane, diethylene glycol monoethyl ether acetate, 1,3-butanediol diacetate, dipropylene glycol methyl ether acetate, diacetone alcohol (also known as 4-hydroxy-4-methyl-2-pentanone), 2-methoxypropyl acetate, 2-methoxy-1-propanol, isopropyl alcohol, etc. However, for environmental reasons, it may be preferable to reduce the amount of aromatic hydrocarbons (benzene, toluene, xylene, ethylbenzene, etc.) as organic solvents (for example, the amount may be set to 50 mass ppm (parts per million) or less, 10 mass ppm or less, or 1 mass ppm or less relative to the total amount of the organic solvent).

[0352] In the present invention, it is preferred to use an organic solvent with a low metal content. For example, the metal content of the organic solvent is preferably 10 parts per billion (ppb) or less. Organic solvents with a ppt (parts per trillion) mass content can be used as needed. These organic solvents are provided, for example, by Toyo Gosei Co., Ltd. (Chemical Industry Daily, November 13, 2015).

[0353] Examples of methods for removing impurities such as metals from organic solvents include distillation (molecular distillation, thin film distillation, etc.) or 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 is preferably made of polytetrafluoroethylene, polyethylene, or nylon.

[0354] The organic solvent may contain isomers (compounds having the same number of atoms but different structures). The isomers may contain only one type or multiple types.

[0355] The content of peroxide in the organic solvent is preferably 0.8 mmol / L or less, and more preferably substantially no peroxide is contained.

[0356] The content of the solvent in the curable composition is preferably 10% by mass to 95% by mass, more preferably 20% by mass to 90% by mass, and even more preferably 30% by mass to 90% by mass.

[0357] Furthermore, from the perspective of environmental regulation, the curable composition of the present invention preferably does not substantially contain environmentally regulated substances. In addition, in the present invention, substantially containing no environmentally regulated substances means that the content of environmentally regulated substances in the curable composition is 50 mass ppm or less, preferably 30 mass ppm or less, more preferably 10 mass ppm or less, and particularly preferably 1 mass ppm or less. Examples of environmentally regulated substances include: benzene; alkylbenzenes such as toluene and xylene; halogenated benzenes such as chlorobenzene, etc. These are registered as environmentally regulated substances under REACH (Registration Evaluation Authorization and Restriction of Chemicals) regulations, PRTR (Pollutant Release and Transfer Register) laws, VOC (Volatile Organic Compounds) regulations, etc., and their usage and handling methods are strictly regulated. When manufacturing the various components used in the curable composition, these compounds are sometimes used as solvents and sometimes mixed into the curable composition as residual solvents. From the perspective of human safety and environmental protection, it is preferred to reduce these substances as much as possible. As a method for reducing environmental control substances, the inside of the system can be heated and decompressed and set to more than the boiling point of the environmental control substances, and a method for removing and reducing environmental control substances by distillation from the inside of the system. In addition, in the case of distilling a small amount of environmental control substances, in order to improve efficiency, it is also useful to azeotrope it with a solvent having the same boiling point as the solvent. In addition, in the case of containing a compound with free radical polymerizability, a polymerization inhibitor can be added and distilled under reduced pressure to remove it, so as to suppress the free radical polymerization reaction during distillation under reduced pressure and cause crosslinking between molecules. These distillation removal methods can be implemented at any stage such as the stage of the raw material, the stage of the reaction product of the raw material (such as the resin solution after polymerization, the multifunctional monomer solution) or the stage of the curable composition made by mixing these compounds.

[0358] <Pigment derivatives>

[0359] The curable composition of the present invention may contain a pigment derivative. The pigment derivative can be used as a dispersing aid, for example. Examples of the pigment derivative include compounds having a structure in which an acid group or a basic group is bonded to a pigment skeleton.

[0360] Examples of the pigment skeleton constituting the pigment derivative include a quinoline pigment skeleton, a benzimidazolone pigment skeleton, a benzisoindole pigment skeleton, a benzothiazole pigment skeleton, an iminium pigment skeleton, a squarylium pigment skeleton, a crotonium pigment skeleton, an oxonol pigment skeleton, a pyrrolopyrrole pigment skeleton, a diketopyrrolopyrrole pigment skeleton, an azo pigment skeleton, an azomethine pigment skeleton, a phthalocyanine pigment skeleton, a naphthalocyanine pigment skeleton, an anthraquinone pigment skeleton, a quinacridone pigment skeleton, a dioxazine pigment skeleton, a perindole pigment skeleton, a perylene pigment skeleton, a thioindigo pigment skeleton, an isoindoline pigment skeleton, an isoindolinone pigment skeleton, a quinophthalone pigment skeleton, a dithiol pigment skeleton, a triarylmethane pigment skeleton, and a pyrromethene pigment skeleton.

[0361] Examples of the acid group include carboxyl, sulfo, phosphoric acid, boric acid, carboxylic acid amide, sulfonic acid amide, imidic acid, and salts thereof. Examples of the atom or atomic group constituting the salt include alkali metal ions (Li + 、Na + , K + etc.), alkaline earth metal ions (Ca 2+ Mg 2+ As the carboxylic acid amide group, preferably -NHCOR X1 As a sulfonamide group, preferably represented by -NHSO2R X2 As the imidic acid group, preferably -SO2NHSO2R X3 、-CONHSO2R X4 、-CONHCOR X5 or SO2NHCOR X6 The group represented by -SO2NHSO2R is more preferably X3 . R X1 ~R X6 R and R are independently an alkyl group or an aryl group. X1 ~R X6 The alkyl group and aryl group represented by the above-mentioned group may have a substituent, and the substituent is preferably a halogen atom, more preferably a fluorine atom.

[0362] Examples of the base include amino, pyridyl and salts thereof, ammonium salts, and phthalimidomethyl groups. Examples of the atom or atomic group constituting the salt include hydroxide ions, halogen ions, carboxylic acid ions, sulfonic acid ions, and phenolate ions.

[0363] Pigment derivatives with excellent visible transparency (hereinafter also referred to as transparent pigment derivatives) can also be used. The maximum value (εmax) of the molar absorption coefficient of the transparent pigment derivative in the wavelength range of 400nm to 700nm is preferably 3,000 L·mol-1 cm -1 Below, more preferably 1,000 L·mol -1 cm -1 Below, more preferably 100 L·mol -1 cm -1 Below. The lower limit of εmax is, for example, 1 L·mol -1 cm -1 Above, can also be 10L·mol -1 cm -1 above.

[0364] Specific examples of pigment derivatives include compounds described in paragraph 0124 of International Publication No. 2022 / 085485, benzimidazolone compounds or salts thereof described in Japanese Patent Application Laid-Open No. 2018-168244, and compounds having an isoindoline skeleton described in general formula (1) in Japanese Patent No. 6996282.

[0365] The content of the pigment derivative is preferably 1 to 30 parts by mass, more preferably 3 to 20 parts by mass, relative to 100 parts by mass of the colorant. Furthermore, the combined content of the pigment derivative and the colorant is preferably 35% by mass or greater, more preferably 40% by mass or greater, even more preferably 45% by mass or greater, and particularly preferably 50% by mass or greater, relative to the total solids content of the curable composition. The upper limit is preferably 70% by mass or less, more preferably 65% ​​by mass or less. The pigment derivative may be used alone or in combination of two or more.

[0366] <Chain transfer agent>

[0367] From the viewpoint of adhesion, the curable composition according to the present invention preferably further contains a chain transfer agent.

[0368] As chain transfer agents, thiol compounds, thiocarbonylthio compounds, dimers of aromatic α-methylalkenyls, etc. can be cited. Thiol compounds are preferred because they can easily adjust the line width of the pattern even with a small amount of compounding. In addition, chain transfer agents are compounds with little coloration.

[0369] Preferably.

[0370] -Mercaptan compounds-

[0371] A thiol compound is a compound having one or more thiol groups. In particular, the curable composition of the present invention preferably contains a compound having two or more thiol groups, i.e., a multifunctional thiol compound. The upper limit of the number of thiol groups contained in the thiol compound is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, particularly preferably 8 or less, and most preferably 6 or less. The lower limit of the number of thiol groups contained in the thiol compound is preferably 3 or more. From the perspective of adhesion, the thiol compound is particularly preferably a compound having four thiol groups.

[0372] Furthermore, the thiol compound is preferably a compound derived from a polyfunctional alcohol.

[0373] The thiol compound is preferably a compound represented by the following formula (SH-1).

[0374] L 1 -(SH) n Formula (SH-1)

[0375] In the formula, SH represents a thiol group, L 1 represents an n-valent group, where n represents an integer of 1 or greater.

[0376] In formula (SH-1), L 1 The n-valent group represented by may include hydrocarbon groups, heterocyclic groups, -O-, -S-, -NR-, -CO-, -COO-, -OCO-, -SO2- or groups composed of combinations thereof. R represents a hydrogen atom, an alkyl group or an aryl group, preferably a hydrogen atom. The hydrocarbon group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Furthermore, the aliphatic hydrocarbon group may be cyclic or non-cyclic. Furthermore, 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. Furthermore, the cyclic aliphatic hydrocarbon group and the aromatic hydrocarbon group may be a monocyclic ring or a condensed ring. The heterocyclic group may be a monocyclic ring or a condensed ring. As the heterocyclic group, a 5-membered ring or a 6-membered ring is preferred. The heterocyclic group may be an aliphatic heterocyclic group or an aromatic heterocyclic group. Furthermore, as heteroatoms constituting the heterocyclic group, nitrogen atoms, oxygen atoms, sulfur atoms, etc. may be mentioned. 1 The number of carbon atoms in is preferably 3-100, more preferably 6-50.

[0377] In formula (SH-1), n ​​represents an integer of 1 or greater. The upper limit of n is preferably 20 or less, more preferably 15 or less, further preferably 10 or less, particularly preferably 8 or less, and most preferably 6 or less. The lower limit of n is preferably 2 or greater, more preferably 3 or greater. n is particularly preferably 4.

[0378] Specific examples of thiol compounds include compounds having the following structures. Commercially available thiol compounds include PEMP (manufactured by SC Organic Chemical Co., Ltd., thiol compound), Sanceler M (manufactured by Sanshin Chemical Industry Co., Ltd., thiol compound), and Karenz MT BD1 (manufactured by SHOWA DENKOK.K., thiol compound).

[0379] [Chemical Formula 29]

[0380]

[0381] [Chemical formula 30]

[0382]

[0383] [Chemical Formula 31]

[0384]

[0385] [Chemical Formula 32]

[0386]

[0387] -Thiocarbonylsulfide compounds-

[0388] The thiocarbonylsulfide compound is a compound having a thiocarbonylsulfide group (-SC(=S)-) in the molecule, and examples thereof include bis(thiocarbonyl)disulfide compounds (compounds represented by the following formula (SC-1)), disulfide ester compounds (compounds represented by the following formula (SC-2)), trithiocarbonate compounds (compounds represented by the following formula (SC-3)), dithiocarbamate compounds (compounds represented by the following formula (SC-4)), and xanthate compounds (compounds represented by the following formula (SC-5)).

[0389] [Chemical Formula 33]

[0390]

[0391] In formula (SC-1) to formula (SC-5), Z 1 ~Z 11 Each independently represents a substituent.

[0392] As Z 1 ~Z 11 The substituents represented by include alkyl, aryl, heteroaryl, -SR Z1 、-NR Z1 R Z2 、-NR Z1-NR Z2 R Z3 、-COOR Z1 、-OCOR Z1 、-CONR Z1 R Z2 、-P(=O)(OR Z1 )2 or -OP(=0)R Z1 R Z2 (Among them, R Z1 、R Z2 and R Z3 Each independently represents an alkyl group, an aryl group, or a heteroaryl group. ) etc. Furthermore, in the above groups, one or more hydrogen atoms bonded to carbon atoms may be substituted by a cyano group, a carboxyl group, or the like.

[0393] The number of carbon atoms in the alkyl group is preferably 1 to 30, more preferably 1 to 15, and even more preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, and is preferably linear or branched.

[0394] The aryl group has preferably 6 to 30 carbon atoms, more preferably 6 to 20 carbon atoms, and even more preferably 6 to 12 carbon atoms.

[0395] The heteroaryl group is preferably a monocyclic heteroaryl group or a condensed heteroaryl group having 2 to 8 rings, more preferably a monocyclic heteroaryl group or a condensed heteroaryl group having 2 to 4 rings. The number of heteroatoms constituting the heteroaryl group's ring is preferably 1 to 3. The heteroatoms constituting the heteroaryl group's ring are preferably nitrogen, oxygen, or sulfur atoms. The heteroaryl group is preferably a 5-membered or 6-membered ring. The number of carbon atoms constituting the heteroaryl group's ring is preferably 3 to 30, more preferably 3 to 18, and even more preferably 3 to 12.

[0396] Specific examples of the bis(thiocarbonyl)disulfide compound include tetraethylaminothiocarbonyl disulfide, tetramethylaminothiocarbonyl disulfide, bis(n-octylmercapto-thiocarbonyl)disulfide, bis(n-dodecylmercapto-thiocarbonyl)disulfide, bis(benzylmercapto-thiocarbonyl)disulfide, bis(n-butylmercapto-thiocarbonyl)disulfide, bis(tert-butylmercapto-thiocarbonyl)disulfide, bis(n-heptylmercapto-thiocarbonyl)disulfide, disulfide, bis(n-hexylmercapto-thiocarbonyl) disulfide, bis(n-pentylmercapto-thiocarbonyl) disulfide, bis(n-nonylmercapto-thiocarbonyl) disulfide, bis(n-decylmercapto-thiocarbonyl) disulfide, bis(tert-dodecylmercapto-thiocarbonyl) disulfide, bis(n-tetradecylmercapto-thiocarbonyl) disulfide, bis(n-hexadecylmercapto-thiocarbonyl) disulfide, bis(n-octadecylmercapto-thiocarbonyl) disulfide, and the like.

[0397] Specific examples of the dithioester compound include 2-phenyl-2-propylbenzodisulfate, 4-cyano-4-(phenylthiocarbonylthio)pentanoic acid, and 2-cyano-2-propylbenzodisulfate.

[0398] Specific examples of the trithiocarbonate compound include S-(2-cyano-2-propyl)-S-dodecyl trithiocarbonate, 4-cyano-4-[(dodecylthio-thiocarbonyl)thio]pentanoic acid, cyanomethyldodecyl trithiocarbonate, and 2-(dodecylthiocarbonylthiothio)-2-methylpropionic acid.

[0399] Specific examples of the dithiocarbamate compound include cyanomethylmethyl(phenyl)carbamoyl disulfate and cyanomethyldiphenylcarbamoyl disulfate.

[0400] Specific examples of the xanthate compound include xanthate esters and the like.

[0401] -Dimer of aromatic α-methylalkenyl-

[0402] Examples of the dimer of aromatic α-methylalkenyl include 2,4-diphenyl-4-methyl-1-pentene.

[0403] Furthermore, as the chain transfer agent, a trithiocarbonate compound that is used as a RAFT agent in RAFT (Reversible Addition-Fragmentation chain Transfer) polymerization, which is one type of living polymerization, can also be preferably used.

[0404] The molecular weight of the chain transfer agent is preferably 200 or more to suppress contamination of the apparatus due to sublimation, etc. The upper limit is preferably 1,000 or less, more preferably 800 or less, and even more preferably 600 or less to increase the SH valence per unit mass.

[0405] From the viewpoint of adhesion, the content of the chain transfer agent is preferably 0.01% to 10% by mass, more preferably 0.01% to 5% by mass, and even more preferably 0.05% to 1% by mass relative to the total solid content of the curable composition. The chain transfer agent may be used alone or in combination of two or more.

[0406] <Polyalkyleneimine>

[0407] The curable composition of the present invention may contain a polyalkyleneimine. The polyalkyleneimine can be used, for example, as a dispersing aid for a pigment. A dispersing aid refers to a material used to improve the dispersibility of a pigment in a curable composition. A polyalkyleneimine is a polymer obtained by ring-opening polymerization of an alkyleneimine and having at least a secondary amino group. In addition to secondary amino groups, the polyalkyleneimine may also contain primary or tertiary amino groups. The polyalkyleneimine is preferably a polymer having a branched structure containing primary, secondary, and tertiary amino groups, respectively. The number of carbon atoms in the alkyleneimine is preferably 2 to 6, more preferably 2 to 4, further preferably 2 or 3, and particularly preferably 2.

[0408] 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, further preferably 10,000 or less, and particularly preferably 2,000 or less. In addition, with respect to the value of the molecular weight of the polyalkyleneimine, when 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, when the molecular weight of the polyalkyleneimine cannot be calculated from the structural formula or is not easy to be calculated from the structural formula, the value of the number average molecular weight measured by the boiling point rise method is used. Furthermore, when the boiling point rise method cannot be measured or is not easy to measure, the value of the number average molecular weight measured by the viscosity method is used. Furthermore, when the viscosity method cannot be measured or is not easy to measure by the viscosity method, the value of the number average molecular weight measured by the polystyrene conversion value measured by GPC (gel permeation chromatography) method is used.

[0409] 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.

[0410] Specific examples of alkyleneimines include ethyleneimine, propyleneimine, 1,2-buteneimine, 2,3-buteneimine, etc., preferably ethyleneimine or propyleneimine, more preferably ethyleneimine. Polyalkyleneimines are particularly preferably polyethyleneimine. In addition, in polyethyleneimine, the primary amino group preferably contains 10 mol% or more, more preferably 20 mol% or more, and further preferably 30 mol% or more relative to the total of primary amino groups, secondary amino groups, and tertiary amino groups. Commercially available products of polyethyleneimines include EPOMIN SP-003, SP-006, SP-012, SP-018, SP-200, and P-1000 (all manufactured by NIPPONSHOKUBAI CO., LTD.).

[0411] The content of the polyalkyleneimine in the total solid content of the curable composition is preferably 0.1% by mass to 5% by mass. The lower limit is more preferably 0.2% by mass or more, further preferably 0.5% by mass or more, and particularly preferably 1% by mass or more. The upper limit is more preferably 4.5% by mass or less, further preferably 4% by mass or less, and particularly preferably 3% by mass or less. Furthermore, the content of the polyalkyleneimine is preferably 0.5% by mass to 20% by mass relative to 100 parts by mass of the pigment. The lower limit is more preferably 0.6% by mass or more, further preferably 1 part by mass or more, and particularly preferably 2 parts by mass or more. The upper limit is more preferably 10 parts by mass or less, further 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, the total amount of these is preferably within the above range.

[0412] <Curing Accelerator>

[0413] The curable composition of the present invention can contain a curing accelerator. As a curing accelerator, a thiol compound, a hydroxymethyl compound, an amine compound, a phosphonium salt compound, an amidine salt compound, an amide compound, a base generator, an isocyanate compound, an alkoxysilane compound, an onium salt compound, etc. can be mentioned. As a specific example of a curing accelerator, the compounds described in paragraph 0164 of International Publication No. 2022 / 085485 can also be used. The content of the curing accelerator in the total solid content of the curable composition is preferably 0.3% to 8.9% by mass, more preferably 0.8% to 6.4% by mass.

[0414] <Infrared absorber>

[0415] The curable composition of the present invention can contain an infrared absorber. For example, when an infrared transmission filter is formed using the curable composition of the present invention, the wavelength of the transmitted light can be shifted to the longer wavelength side by including an infrared absorber in the curable composition. The infrared absorber is preferably a compound having a maximum absorption wavelength on a wavelength side longer than 700 nm. The infrared absorber is preferably a compound having a maximum absorption wavelength in a range exceeding 700 nm and below 1800 nm. Furthermore, the absorbance A of the infrared absorber at a wavelength of 500 nm is preferably 0.1%. 1 and the absorbance A at the maximum absorption wavelength 2 A 1 / A 2 It is preferably 0.08 or less, and more preferably 0.04 or less.

[0416] Examples of infrared absorbers include pyrrolopyrrole compounds, cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, quaterrylene compounds, merocyanine compounds, crotonium compounds, oxocyanine compounds, iminium compounds, dithiol compounds, triarylmethane compounds, pyrromethene compounds, azomethine compounds, anthraquinone compounds, dibenzofuranone compounds, dithiol metal complexes, metal oxides, and metal borides. Specifically, the compounds described in paragraphs 0114 to 0121 of International Publication No. 2022 / 065215, the compounds described in paragraphs 0144 to 0146 of International Publication No. 2021 / 049441, the croconic acid compounds described in Japanese Patent Application Laid-Open No. 2021-195515, the near-infrared absorbing pigments described in Japanese Patent Application Laid-Open No. 2022-022070, and the crotonium compounds described in International Publication No. 2019 / 021767 can also be used.

[0417] The content of the infrared absorber in the total solid content of the curable composition is preferably 1% to 40% by mass. The lower limit is more preferably 2% by mass or more, further preferably 5% by mass or more, and particularly preferably 10% by mass or more. The upper limit is more preferably 30% by mass or less, further preferably 25% by mass or less. The curable composition involved in the present invention may contain only one infrared absorber or may contain two or more. When containing two or more infrared absorbers, the total amount of these is preferably within the above range.

[0418] <Ultraviolet absorber>

[0419] The curable composition of the present invention can contain an ultraviolet absorber. As ultraviolet absorbers, conjugated diene compounds, aminodiene compounds, salicylate compounds, benzophenone compounds, benzotriazole compounds, acrylonitrile compounds, hydroxyphenyltriazine compounds, indole compounds, triazine compounds, etc. can be mentioned. As specific examples of these compounds, the compounds described in paragraph 0179 of International Publication No. 2022 / 085485 can also be used. As ultraviolet absorbers, reactive triazine ultraviolet absorbers described in Japanese Patent Application Laid-Open No. 2021-178918 and ultraviolet absorbers described in Japanese Patent Application Laid-Open No. 2022-007884 can be used. The content of ultraviolet absorbers in the total solid content of the curable composition is preferably 0.01% to 10% by mass, more preferably 0.01% to 5% by mass. Ultraviolet absorbers can be used alone or in combination. When using two or more, the total amount thereof is preferably within the above range.

[0420] <Polymerization Inhibitor>

[0421] The curable composition of the present invention can contain a polymerization inhibitor. As the polymerization inhibitor, 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-tert-butylphenol), N-nitrosophenylhydroxylamine salt (ammonium salt, cerium salt, etc.) can be mentioned. Among them, p-methoxyphenol is preferred. The content of the polymerization inhibitor in the total solid content of the curable composition is preferably 0.0001% by mass to 5% by mass. The polymerization inhibitor may be only one kind or two or more kinds. In the case of two or more kinds, the total amount of these is preferably within the above range.

[0422] <Silane coupling agent>

[0423] The curable composition of the present invention may contain a silane coupling agent. In the present invention, a silane coupling agent refers to a silane compound having a hydrolyzable group and other functional groups. Furthermore, a hydrolyzable group refers to a substituent that directly bonds to a silicon atom and can produce a siloxane bond through at least one of a hydrolysis reaction and a condensation reaction. Examples of hydrolyzable groups include halogen atoms, alkoxy groups, and acyloxy groups, with alkoxy groups being preferred. That is, the silane coupling agent is preferably a compound having an alkoxysilyl group.

[0424] Furthermore, as functional groups other than hydrolyzable groups, for example, vinyl, (meth) allyl, (meth) acryloyl, mercapto, epoxy, oxetane, amino, urea, thioether, isocyanate, phenyl, etc. can be mentioned, preferably amino, (meth) acryloyl and epoxy. As specific examples of silane coupling agents, the compounds described in paragraph 0177 of International Publication No. 2022 / 085485 can also be used. The content of the silane coupling agent in the total solid content of the curable composition is preferably 0.01% by mass to 15.0% by mass, more preferably 0.05% by mass to 10.0% by mass.

[0425] The silane coupling agent may be used alone or in combination of two or more. In the case of two or more silane coupling agents, the total amount thereof is preferably within the above range.

[0426] <Surfactant>

[0427] The curable composition of the present invention may contain a surfactant. Examples of surfactants include fluorochemical surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and silicone surfactants. The surfactant is preferably a silicone surfactant or a fluorochemical surfactant. For surfactants, reference may be made to the surfactants described in paragraphs 0238 to 0245 of International Publication No. 2015 / 166779, which is incorporated herein by reference.

[0428] The fluorine content in the fluorine-based surfactant is preferably 3% to 40% by mass, more preferably 5% to 30% by mass, and particularly preferably 7% to 25% by mass. Fluorine-based surfactants with a fluorine content within this range are effective in achieving uniform thickness of the coating film and saving liquid, and also have good solubility in the curable composition.

[0429] As the fluorine-based surfactant, the compounds described in paragraphs 0167 to 0173 of International Publication No. 2022 / 085485, the fluorinated copolymers described in Japanese Patent Application Laid-Open No. 2022-000494, and the like can also be used.

[0430] As the nonionic surfactant, the compounds described in paragraph 0174 of International Publication No. 2022 / 085485 can also be used.

[0431] Examples of silicone surfactants include DOWSIL SH8400, SH8400 FLUID, FZ-2122, 67 Additive, 74 Additive, M Additive, and SF 8419 OIL (all manufactured by Dow Corning Toray Co., Ltd.), TSF-4300, TSF-4445, TSF-4460, and TSF-4452 (all manufactured by Momentive Performance Materials Inc.), KP-341, KF-6000, KF-6001, KF-6002, and 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), etc.

[0432] Furthermore, as the silicone surfactant, a compound having the following structure may be used: wherein n is 1 to 200.

[0433] [Chemical Formula 34]

[0434]

[0435] 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 only one type or two or more types. In the case of two or more types, the total amount of these is preferably within the above range.

[0436] <Antioxidants>

[0437] The curable composition involved in the present invention can contain an antioxidant. Examples of the antioxidant include phenol compounds, phosphite compounds, thioether compounds, and the like. As the phenol compound, any phenol compound known as a phenol-based antioxidant can be used. Preferred phenol compounds include hindered phenol compounds. Preferably, the compound has a substituent at a position adjacent to the phenolic hydroxyl group (ortho position). As the above-mentioned substituent, a substituted or unsubstituted alkyl group having 1 to 22 carbon atoms is preferred. Furthermore, the antioxidant is preferably a compound having a phenol group and a phosphite group in the same molecule. Furthermore, the antioxidant can also preferably use a phosphorus-based antioxidant. Examples of the phosphorus-based antioxidant include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetrakis-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-2-yl)oxy]ethyl]amine, and bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite. Commercially available antioxidants include, for example, ADEKA STAB AO-20, ADEKA STAB AO-30, ADEKA STAB AO-40, ADEKA STAB AO-50, ADEKA STAB AO-50F, ADEKA STAB AO-60, ADEKA STAB AO-60G, ADEKA STAB AO-80, and ADEKA STAB AO-330 (all manufactured by ADEKA CORPORATION). Furthermore, antioxidants may include compounds described in paragraphs 0023 to 0048 of Japanese Patent No. 6268967, compounds described in International Publication No. 2017 / 006600, compounds described in International Publication No. 2017 / 164024, and 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% by mass to 20% by mass, more preferably 0.3% by mass to 15% by mass. Only one antioxidant may be used, or two or more antioxidants may be used. When two or more antioxidants are used, the total amount thereof is preferably within the above range.

[0438] <Other ingredients>

[0439] The curable composition involved in the present invention can contain sensitizer, curing accelerator, filler, thermosetting accelerator, plasticizer and other auxiliary agents (for example, conductive particles, defoamer, flame retardant, leveling agent, peeling accelerator, spices, surface tension modifier etc.) as needed. By suitably containing these ingredients, the properties such as film physical properties can be adjusted. These ingredients can also use the compound recorded in paragraph 0182 of International Publication No. 2022 / 085485, the epoxy resin recorded in Japanese Patent Application Laid-Open No. 2021-195421 Gazette, the epoxy resin recorded in Japanese Patent Application Laid-Open No. 2021-195422 Gazette etc.

[0440] The curable composition of the present invention may contain a metal oxide to adjust the refractive index of the resulting film. Examples of the metal oxide include TiO2, ZrO2, Al2O3, and SiO2. The primary particle size of the metal oxide is preferably 1 nm to 100 nm, more preferably 3 nm to 70 nm, and even more preferably 5 nm to 50 nm. The metal oxide may have a core-shell structure. In this case, the core may be hollow.

[0441] The curable composition of the present invention may contain a light resistance improver. As the light resistance improver, the compounds described in paragraph 0183 of International Publication No. 2022 / 085485 may also be used.

[0442] The curable composition of the present invention also preferably contains substantially no terephthalate. Here, "substantially no terephthalate" means that the content of terephthalate in the total amount of the curable composition is 1000 ppb by mass or less, more preferably 100 ppb by mass or less, and particularly preferably zero (0).

[0443] The content of melamine in the curable composition of the present invention is preferably low. Specifically, the content of melamine is preferably 10,000 ppm by mass or less, and may be 0 (zero), based on the total amount of the curable composition.

[0444] From the perspective of environmental regulation, the use of perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts is sometimes regulated. In the curable composition involved in the present invention, when the content of the above-mentioned compounds is reduced, the content of perfluoroalkylsulfonic acid (especially perfluoroalkylsulfonic acid having a perfluoroalkyl group with 6 to 8 carbon atoms) and its salts and perfluoroalkylcarboxylic acid (especially perfluoroalkylcarboxylic acid having a perfluoroalkyl group with 6 to 8 carbon atoms) and its salts is preferably in the range of 0.01ppb to 1,000ppb, more preferably in the range of 0.05ppb to 500ppb, and further preferably in the range of 0.1ppb to 300ppb, relative to the total solid content of the curable composition. The curable composition involved in the present invention may also be substantially free of perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts. For example, by using a compound that can serve as a substitute for perfluoroalkylsulfonic acid and its salts and a compound that can serve as a substitute for perfluoroalkylcarboxylic acid and its salts, a curable composition that substantially does not contain perfluoroalkylsulfonic acid and its salts and perfluoroalkylcarboxylic acid and its salts can also be selected. Compounds that can serve as alternatives to regulated compounds include, for example, compounds that are excluded from regulation based on the number of carbon atoms in their perfluoroalkyl groups. However, the above does not preclude the use of perfluoroalkylsulfonic acids and their salts, and perfluoroalkylcarboxylic acids and their salts. The curable composition of the present invention may also contain perfluoroalkylsulfonic acids and their salts, and perfluoroalkylcarboxylic acids and their salts within the maximum allowable range.

[0445] The water content of the curable composition of the present invention is preferably 3% by mass or less, more preferably 0.01% by mass to 1.5% by mass, and even more preferably 0.1% by mass to 1.0% by mass. The water content can be measured by the Karl Fischer method.

[0446] The curable composition of the present invention can be used by adjusting the viscosity for purposes such as adjusting the film surface shape (flatness, etc.) and adjusting the film thickness. The viscosity value can be appropriately selected as needed, for example, preferably 0.3 mPa·s to 50 mPa·s at 25°C, and more preferably 0.5 mPa·s to 20 mPa·s. As a method for measuring the viscosity, for example, a cone-plate viscometer can be used and measured at a temperature of 25°C.

[0447] Regarding the curable composition involved in the present invention, from the perspectives of environmental considerations, suppression of foreign matter generation, and suppression of device contamination, the chloride ion content in the curable composition is preferably 10,000 ppm or less, and more preferably 1000 ppm or less. In order to bring the chloride ion content in the curable composition within the above range, methods such as using raw materials with a low chloride ion content and removing chloride ions by water washing, ion exchange resin, filtration, etc. can be used. As a method for measuring chloride ions, known methods can be used, for example, ion chromatography, combustion ion chromatography, etc.

[0448] <Storage Container>

[0449] The container for storing the curable composition is not particularly limited, and a known container can be used. In addition, the container described in paragraph 0187 of International Publication No. 2022 / 085485 can also be used.

[0450] <Method for Preparing Curable Composition>

[0451] The curable composition of the present invention can be prepared by mixing the above-mentioned components. When preparing the curable composition, all the components can be dissolved and / or dispersed in a solvent at the same time to prepare the curable composition. Alternatively, each component can be appropriately divided into two or more solutions or dispersions as needed and mixed at the time of use (during application) to prepare the curable composition.

[0452] Furthermore, when preparing the curable composition, it is preferred to include a process for dispersing the pigment. In the pigment dispersion process, as the mechanical force for dispersing the pigment, compression, extrusion, impact, shearing, pitting, etc. can be enumerated. As specific examples of these processes, bead milling, sand milling, roller milling, ball milling, paint stirring, micro jet, high-speed impeller, sand mixing, jet mixing, high-pressure wet micronization, ultrasonic dispersion, etc. can be enumerated. Furthermore, in the pulverization of the pigment in the sand mill (bead mill), it is preferably processed under conditions that improve the pulverization efficiency by using microbeads with a small diameter, increasing the filling rate of microbeads, etc. Furthermore, after the pulverization process, it is preferably removed by filtration, centrifugation, etc. Furthermore, regarding the pigment dispersion process and disperser, the processes and dispersers described in "Complete Collection of Dispersion Technology, Published by JOHOKIKO CO., LTD., July 15, 2005," "Comprehensive Data Collection of Dispersion Technology and Practical Industrial Applications Focusing on Suspensions (Solid / Liquid Dispersion Systems), Published by the Business Development Center Publishing Department, October 10, 1978," and paragraph 0022 of Japanese Patent Application Publication No. 2015-157893 can be preferably used. Furthermore, in the pigment dispersion process, the particles can be refined by a salt milling process. For the materials, apparatus, and processing conditions used in the salt milling process, reference can be made to the descriptions of Japanese Patent Application Publication No. 2015-194521 and Japanese Patent Application Publication No. 2012-046629, for example. As microbeads used for dispersion, zirconium oxide, agate, quartz, titanium dioxide, tungsten carbide, silicon nitride, aluminum oxide, stainless steel, glass, or a combination thereof can be used. Furthermore, it is possible to use an inorganic compound having a Mohs hardness of 2 or higher. The above beads may be contained in the composition in an amount of 1 to 10,000 ppm.

[0453] When preparing a curable composition, it is preferred to filter the curable composition to remove foreign matter, reduce defects, etc. The filters and filtration methods described in paragraphs 0196 to 0199 of International Publication No. 2022 / 085485 can also be used.

[0454] (cured product and film)

[0455] The cured product according to the present invention is a cured product obtained by curing the curable composition according to the present invention.

[0456] The film involved in the present invention is preferably a film obtained by the curable composition involved in the present invention, a film formed by curing the curable composition involved in the present invention. The film involved in the present invention can be used for filters such as color filters and infrared transmission filters. Specifically, it can be preferably used as a colored pixel of a color filter. As colored pixels, red pixels, green pixels, blue pixels, magenta pixels, cyan pixels, yellow pixels, etc. can be mentioned, preferably green pixels, blue pixels, more preferably green pixels.

[0457] The thickness of the film of the present invention can be adjusted appropriately depending on the intended purpose, but is preferably 0.1 μm to 20 μm. The upper limit of the film thickness is more preferably 10 μm or less, even more preferably 5 μm or less, particularly preferably 3 μm or less, and most preferably 1.5 μm or less. The lower limit of the film thickness is more preferably 0.2 μm or more, even more preferably 0.3 μm or more.

[0458] (Method for producing a cured product and method for producing a film)

[0459] The method for producing the cured product and the method for producing the film of the present invention are not particularly limited, but preferably include a step of irradiating the curable composition of the present invention with light having a wavelength of 150 nm to 300 nm.

[0460] Examples of light having a wavelength of 150 nm to 300 nm include KrF rays (wavelength: 248 nm) and ArF rays (wavelength: 193 nm).

[0461] Furthermore, the light having a wavelength of 150 nm to 300 nm is preferably excimer laser light.

[0462] The shape of the obtained cured product is not particularly limited, but is preferably a film.

[0463] The film of the present invention can be produced by applying the curable composition of the present invention to a support. The film production method preferably further includes a step of forming a pattern (pixel). Examples of methods for forming the pattern (pixel) include photolithography and dry etching, with photolithography being preferred.

[0464] Pattern formation using photolithography preferably 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 a pattern, and developing and removing the unexposed portions of the curable composition layer to form a pattern (pixels). Alternatively, a step of baking the curable composition layer (pre-baking step) and a step of baking the developed pattern (pixels) (post-baking step) may be provided as needed.

[0465] In the process of forming a curable composition layer, a curable composition according to the present invention is used to form a curable composition layer on a support. The support is not particularly limited and can be appropriately selected according to the application. For example, a glass substrate, a silicon substrate, etc. can be mentioned, preferably a silicon substrate. In addition, a charge coupled device (CCD), a complementary metal oxide semiconductor (CMOS), a transparent conductive film, etc. can be formed on the silicon substrate. In addition, a black matrix is ​​sometimes formed on the silicon substrate to isolate each pixel. In addition, in order to improve the adhesion with the upper layer, prevent the diffusion of substances, or flatten the surface of the substrate, a base layer can be provided on the silicon substrate. The base layer can be formed using a composition obtained by removing a colorant from the curable composition described in this specification or a composition comprising a resin, a polymerizable compound, a surfactant, etc. described in this specification. When measured with diiodomethane, the surface contact angle of the base layer is preferably 20° to 70°. In addition, the surface contact angle of the base layer is preferably 30° to 80° when measured in water.

[0466] As a method for applying the curable composition, a known method may be used. For example, the method described in paragraph 0207 of International Publication No. 2022 / 085485 may also be used.

[0467] The curable composition layer formed on the support can be dried (prebaked). When the film is manufactured by a low temperature process, prebaking is not required. When prebaking is performed, the prebaking temperature is preferably 150°C or less, more preferably 120°C or less, and further preferably 110°C or less. The lower limit can be set to, for example, 50°C or more, or 80°C or more. The prebaking time is preferably 10 seconds to 300 seconds, more preferably 40 seconds to 250 seconds, and further preferably 80 seconds to 220 seconds. Prebaking can be performed using a hot plate, an oven, or the like.

[0468] Next, the curable composition layer is exposed to light in a pattern (exposure step). For example, the curable composition layer is exposed to light through a mask having a predetermined mask pattern using a stepper or scanner exposure machine, thereby exposing the curable composition layer to a pattern. Thus, the exposed portion can be cured.

[0469] Examples of radiation (light) that can be used for exposure include g-rays and i-rays. Furthermore, light with a wavelength of 300 nm or less (preferably light with a wavelength of 150 nm to 300 nm) can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm), with KrF rays (wavelength 248 nm) being preferred. Furthermore, long-wavelength light sources with wavelengths of 300 nm or greater can also be used.

[0470] Furthermore, during exposure, light can be irradiated continuously or pulsed (pulse exposure). Pulse exposure refers to an exposure method in which light is irradiated and paused repeatedly with a short period (e.g., milliseconds or less) as a cycle to perform exposure.

[0471] The irradiation dose (exposure dose) is preferably 0.03 J / cm 2 ~2.5J / cm 2 , more preferably 0.05 J / cm 2 ~1.0J / cm 2 The oxygen concentration during exposure can be appropriately selected. In addition to being performed in the atmosphere, exposure can also be performed in a low-oxygen environment with an oxygen concentration of 19% by volume or less (for example, 15% by volume, 5% by volume, or substantially oxygen-free), or in a high-oxygen environment with an oxygen concentration exceeding 21% by volume (for example, 22% by volume, 30% by volume, or 50% by volume). Furthermore, the exposure illuminance can be appropriately set and can generally be selected from 1000 W / m 2 ~100000W / m 2 (For example, 5000W / m 2 、15000W / m 2 or 35000W / m 2 The oxygen concentration and exposure illuminance conditions can be appropriately combined, for example, the oxygen concentration can be set to 10% by volume and the illuminance can be set to 10000 W / m 2 , oxygen concentration is 35% by volume and illumination is 20000W / m 2 wait.

[0472] Next, the unexposed portion of the curable composition layer is removed by development to form a pattern (pixel). The unexposed portion of the curable composition layer can be removed by development using a developer. As a result, the unexposed portion of the curable composition layer in the exposure process is dissolved into the developer, and only the photocured portion remains. The temperature of the developer is preferably 20°C to 30°C, for example. The development time is preferably 20 seconds to 180 seconds. In addition, in order to improve the residue removability, the following process can be repeated multiple times: the developer is discarded every 60 seconds, and a new developer is supplied.

[0473] Examples of the developer include organic solvents and alkaline developers, and alkaline developers are preferably used. The developer and development method described in paragraph 0214 of International Publication No. 2022 / 085485 can also be used.

[0474] After development, it is preferred to perform additional exposure treatment and heating treatment (post-baking) after drying. Additional exposure treatment and post-baking are curing treatments performed after development, which are used to make the curing more complete. The heating temperature in post-baking is preferably 100°C to 240°C, for example, and more preferably 200°C to 240°C. The developed film can be post-dried in a continuous or batch manner using a heating mechanism such as a hot plate or a convection oven (hot air circulation dryer), a high-frequency heater, etc. in such a manner as to achieve the above conditions. In the case of performing additional exposure treatment, the light used for exposure is preferably light with a wavelength of 400nm or less. In addition, the additional exposure treatment can be performed by the method described in Korean Patent Gazette No. 10-2017-0122130.

[0475] When patterning is performed by dry etching, the method described in paragraph 0216 of International Publication No. 2022 / 085485 can also be used.

[0476] (Optical Components)

[0477] The optical element according to the present invention includes the film according to the present invention.

[0478] Examples of the optical element include optical filters, lenses, prisms, reflecting mirrors, and diffraction gratings. Among these, optical filters are preferred.

[0479] Examples of the type of optical filter include color filters and infrared transmission filters, and color filters are preferred. The color filter preferably has the film according to the present invention as its colored pixel.

[0480] In optical filters, the film thickness of the film of the present invention can be adjusted appropriately depending on the intended purpose. The film 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 film thickness is preferably 0.1 μm or more, more preferably 0.2 μm or more, and even more preferably 0.3 μm or more.

[0481] The width of the pixels included in the filter is preferably 0.4 μm to 10.0 μm. The lower limit is more preferably 0.4 μm or greater, further preferably 0.5 μm or greater, and particularly preferably 0.6 μm or greater. The upper limit is more preferably 5.0 μm or less, further preferably 2.0 μm or less, particularly preferably 1.0 μm or less, and most preferably 0.8 μm or less. Furthermore, the Young's modulus of the pixel is preferably 0.5 GPa to 20 GPa, and more preferably 2.5 GPa to 15 GPa.

[0482] Each pixel included in the filter preferably has high flatness. Specifically, the surface roughness Ra of the pixel is preferably less than 100 nm, more preferably less than 40 nm, and further preferably less than 15 nm. There is no regulation on the lower limit, for example, it is preferably more than 0.1 nm. Regarding the surface roughness of the pixel, it can be measured using, for example, AFM (atomic force microscope) Dimension3100 manufactured by Veeco. In addition, the water contact angle on the pixel can be set to an appropriate preferred value, usually in the range of 50° to 110°. For example, the contact angle can be measured using a contact angle meter CV-DT·A type (manufactured by Kyowa Interface Science Co., LTD.). In addition, the volume resistance value of the pixel is preferably high. Specifically, the volume resistance value of the pixel is preferably 10 9 Ω·cm or more, more preferably 10 11 Ω·cm or more. The upper limit is not specified, for example, it is preferably 10 14 The volume resistance value of the pixel can be measured using an ultra-high resistance meter 5410 (manufactured by ADVANTEST CORPORATION).

[0483] In the optical filter, a protective layer may also be provided on the surface of the film involved in the present invention. By providing a protective layer, various functions such as oxygen blocking, low reflectivity, hydrophilicity and hydrophobicity, and shielding of light of specific wavelengths (ultraviolet rays, near-infrared rays, etc.) can be imparted. The thickness of the protective layer is preferably 0.01 μm to 10 μm, and more preferably 0.1 μm to 5 μm. As methods for forming the protective layer, a method of forming it by coating a protective layer-forming composition, a chemical vapor deposition method, and a method of attaching a formed resin with an adhesive material can be cited. As the components constituting the protective layer, (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, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, polyol resin, polyvinylidene chloride resin, melamine resin, polyurethane resin, polyaramid resin, polyamide resin, alkyd resin, epoxy resin, modified silicone resin, fluororesin, polyacrylonitrile resin, cellulose resin, Si, C, W, Al2O3, Mo, SiO2, Si2N4, etc., can contain two or more of these components. For example, in the case of a protective layer for the purpose of blocking oxygen, the protective layer preferably includes polyol resin, SiO2 and Si2N4. In addition, in the case of a protective layer for the purpose of low reflectivity, the protective layer preferably includes (meth) acrylic resin and fluororesin.

[0484] The protective layer may contain organic / inorganic particles, absorbents of light of a specific wavelength (e.g., ultraviolet rays, near infrared rays, etc.), refractive index regulators, antioxidants, adhesives, surfactants and other additives as needed. Examples of organic / inorganic particles include polymer particles (e.g., silicone resin particles, polystyrene particles, melamine resin particles), titanium oxide, zinc oxide, zirconium oxide, indium oxide, aluminum oxide, titanium nitride, titanium oxynitride, magnesium fluoride, hollow silica, silicon dioxide, calcium carbonate, barium sulfate, etc. Known absorbents can be used as absorbents of light of a specific wavelength. The content of these additives can be appropriately adjusted, preferably 0.1% to 70% by mass, and more preferably 1% to 60% by mass, relative to the total mass of the protective layer.

[0485] Furthermore, as the protective layer, the protective layer described in paragraphs 0073 to 0092 of Japanese Patent Application Laid-Open No. 2017-151176 may also be used.

[0486] The optical filter may have a structure in which pixels are embedded in spaces partitioned into a grid shape by partition walls, for example.

[0487] (Image Sensor)

[0488] The image sensor according to the present invention includes the film of the present invention.

[0489] Examples of the image sensor include solid-state imaging elements, X-ray imaging elements, and organic thin-film imaging elements. Among them, solid-state imaging elements can be preferably used.

[0490] The solid-state imaging element according to the present invention includes the film according to the present invention. The structure of the solid-state imaging element is not particularly limited as long as it functions as a solid-state imaging element, and examples thereof include the following structures.

[0491] Specifically, a substrate includes a transfer electrode composed of multiple photodiodes and polysilicon, which form the light-receiving area of ​​a solid-state imaging element (CCD (charge-coupled device) image sensor, CMOS (complementary metal oxide semiconductor) image sensor, etc.); a light-shielding film with an opening only for the light-receiving portion of the photodiode is provided on the photodiode and the transfer electrode; a device protection film composed of silicon nitride, etc., formed to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode is provided on the light-shielding film; and a color filter is provided on the device protection film. Alternatively, a structure may be provided in which a focusing mechanism (e.g., a microlens, etc., the same applies hereinafter) is provided on the device protection film and below the color filter (on the side closer to the substrate), or a structure may be provided in which a focusing mechanism is provided on the color filter.

[0492] Furthermore, the color filter may also have a structure in which, for example, each colored pixel is embedded in a space divided into a grid shape by a partition wall. Preferably, the refractive index of the partition wall at this time is lower than that of each colored pixel. As examples of imaging devices having these structures, devices described in Japanese Patent Application Publication No. 2012-227478, Japanese Patent Application Publication No. 2014-179577, and International Publication No. 2018 / 043654 may be cited. Furthermore, as shown in Japanese Patent Application Publication No. 2019-211559, an ultraviolet absorption layer may be provided in the structure of the solid-state imaging element to improve light resistance. In addition to being used as a digital camera, an electronic device with a camera function (such as a mobile phone), the imaging device having the solid-state imaging element of the present invention may also be used as a vehicle-mounted camera or a surveillance camera.

[0493] (Image Display Device)

[0494] The image display device involved in the present invention includes the film involved in the present invention. As the image display device, a liquid crystal display device, an organic electroluminescent display device, etc. can be cited. The definition of the image display device and the details of each image display device are recorded in, for example, "Electronic Display Device (written by Akio Sasaki, Kogyo Chosakai Publishing Co., Ltd., published in 1990)", "Display Device (written by Junsho Ibuki, Sangyo Tosho Publishing Co., Ltd., published in 1989)", etc. In addition, regarding the liquid crystal display device, it is recorded in, for example, "Next Generation Liquid Crystal Display Technology (edited by Tatsuo Uchida, Kogyo Chosakai Publishing Co., Ltd., published in 1994)". There is no particular limitation on the liquid crystal display device to which the present invention can be applied. For example, it can be applied to liquid crystal display devices of various types described in the above-mentioned "Next Generation Liquid Crystal Display Technology".

[0495] Example

[0496] Below, give embodiment and the present invention is further described in detail.The material, usage amount, ratio, processing content, processing sequence etc. shown in the following examples can be appropriately changed as long as they do not depart from the purport of the present invention.Therefore, the scope of the present invention is not limited to the specific example shown below.

[0497] Furthermore, in the present examples, "%" and "parts" respectively represent "mass %" and "mass parts" unless otherwise specified.

[0498] In addition, A-1 to A-78 of the compound (A) used in the examples are the same compounds as the radical polymerization initiators A-1 to A-78 described above as specific examples of the compound (A), respectively.

[0499] <Example 1: Preparation of red curable composition>

[0500] [Preparation of Red Pigment Dispersion 1]

[0501] The following composition mixture was uniformly stirred and mixed, and then dispersed for 5 hours using zirconia beads with a diameter of 1 mm using an Eiger mill ("MINIMODEL M-250MKII" manufactured by EIGER-JAPAN Co., Ltd.), and then filtered through a 5 μm filter to prepare a red pigment dispersion 1.

[0502] Colorant (a mixture of equal parts of CI Pigment Red 254, CI Pigment Red 272, and CI Pigment Red 139): 60.1 parts

[0503] Pigment derivative (Syn-1): 10.2 parts

[0504] Resin (B1) (C2-1) having a graft chain and a crosslinking group: 20 parts

[0505] Solvent (propylene glycol monomethyl ether acetate): 350 parts

[0506] [Preparation of Curable Composition]

[0507] The following compositions were mixed to prepare a curable composition of Example 1.

[0508] Red pigment dispersion 1: 440.3 parts

[0509] Resin (alkali-soluble resin) (B-1): 5 parts

[0510] Radical curable compound (C1-1) with a molecular weight of less than 3000: 7.0 parts

[0511] Compound (A) (A-1): 3.0 parts

[0512] Epoxy compound (EHPE-3150, manufactured by Daicel Corporation): 0.02 parts

[0513] Ultraviolet absorber (Tinuvin 326, manufactured by BASF): 0.01 part

[0514] Surfactant (KF-6001 (carbinol-modified polydimethylsiloxane at both ends, manufactured by Shin-Etsu Chemical Co., Ltd.)): 0.01 parts by mass

[0515] Polymerization inhibitor (p-methoxyphenol): 0.01 part

[0516] Solvent (propylene glycol monomethyl ether acetate): 50 parts

[0517] <Examples 2 to 94 and Comparative Examples 1 to 7: Preparation of Red Curable Compositions>

[0518] As described in Tables 1 to 7 below, pigment dispersions were prepared in the same manner as in Example 1 using the respective components, and curable compositions were prepared using the obtained pigment dispersions.

[0519] In addition, although epoxy compounds, ultraviolet absorbers, surfactants, and polymerization inhibitors are not described in Tables 1 to 7, the curable compositions of Examples 2 to 94 and Comparative Examples 1 to 7 contain the same epoxy compounds, ultraviolet absorbers, surfactants, and polymerization inhibitors as those in Example 1 in the same amounts as those in Example 1.

[0520] Furthermore, as described in Tables 1 to 7, when two or more colorants, solvents, or curable compounds (C1) were used, they were all mixed in equal amounts. Furthermore, as described in Tables 1, 3, and 4, when compound (A) and a comparative compound were used simultaneously, they were also used in equal amounts.

[0521] [Table 1]

[0522]

[0523] [Table 2]

[0524]

[0525] [Table 3]

[0526]

[0527] [Table 4]

[0528]

[0529] [Table 5]

[0530]

[0531] [Table 6]

[0532]

[0533] [Table 7]

[0534]

[0535] The details of the components used in the curable composition are as follows.

[0536] <Colorant>

[0537] PR254: CI Pigment Red 254 [diketopyrrolopyrrole compound, red pigment (R pigment)]

[0538] PR272: CI Pigment Red 272 [diketopyrrolopyrrole compound, red pigment (R pigment)]

[0539] PR291: CI Pigment Red 291 [brominated diketopyrrolopyrrole compound, red pigment (R pigment)]

[0540] PR177: CI Pigment Red 177 [anthraquinone compound, red pigment (R pigment)]

[0541] PR264: CI Pigment Red 264 [diketopyrrolopyrrole compound, red pigment (R pigment)]

[0542] PR291: CI Pigment Red 291 [brominated diketopyrrolopyrrole compound, red pigment (R pigment)]

[0543] PG36: CI Pigment Green 36 [copper phthalocyanine complex, green pigment (G pigment)]

[0544] PG58: CI Pigment Green 58 [zinc phthalocyanine complex, green pigment (G pigment)]

[0545] PY129: CI Pigment Yellow 129 [azomethine copper complex, yellow pigment (Y pigment)]

[0546] PY138: CI Pigment Yellow 138 [quinophthalone compound, yellow pigment (Y pigment)]

[0547] PY139: CI Pigment Yellow 139 [isoindoline compound, yellow pigment (Y pigment)]

[0548] PY150: CI Pigment Yellow 150 [monoazo compound, yellow pigment (Y pigment)]

[0549] PY185: CI Pigment Yellow 185 [isoindoline compound, yellow pigment (Y pigment)]

[0550] PY215: CI Pigment Yellow 215 [pteridine compound, yellow pigment (Y pigment)]

[0551] PB15:6:CI Pigment Blue 15:6 [Copper phthalocyanine complex, blue pigment (B pigment)]

[0552] PV23: CI Pigment Violet 23 [dioxazine compound, purple pigment (B pigment)]

[0553] P-1: A compound having the following structure (diketopyrrolopyrrole boron complex, wherein Me represents a methyl group and Ph represents a phenyl group.)

[0554] [Chemical Formula 35]

[0555]

[0556] P-2: Compound of the following structure (squaric acid pigment)

[0557] [Chemical Formula 36]

[0558]

[0559] P-3: Black pigment (titanium black (TiOxNy) manufactured by Mitsubishi Materials Corporation)

[0560] P-4: White pigment (titanium oxide (TTO-51(C)) manufactured by ISHIHARA SANGYO KAISHA, LTD.)

[0561] P-5: Compound having the following structure (carmine dye, a compound described in Japanese Patent Application Laid-Open No. 2018-141173)

[0562] [Chemical Formula 37]

[0563]

[0564] <Pigment derivatives>

[0565] Syn-1~Syn-7: Compounds with the following structures

[0566] [Chemical Formula 38]

[0567]

[0568] [Chemical Formula 39]

[0569]

[0570] <Resin (B1) and Comparative Resins>

[0571] C2-1: Resin with the following structure (Mw 20,000, acid value 67 mgKOH / g)

[0572] [Chemical Formula 40]

[0573]

[0574] C2-2: Resin with the following structure (Mw 23,000, acid value 59 mgKOH / g)

[0575] [Chemical Formula 41]

[0576]

[0577] C2-3: Resin with the following structure (Mw 18,000, acid value 69 mgKOH / g)

[0578] [Chemical Formula 42]

[0579]

[0580] C2-4: Resin with the following structure (the values ​​indicated on the main chain are molar ratios. Mw: 23,000, acid value: 67 mgKOH / g)

[0581] [Chemical Formula 43]

[0582]

[0583] C2-5: Resin with the following structure (Mw 10,000, acid value 85 mgKOH / g)

[0584] [Chemical Formula 44]

[0585]

[0586] C2-6: Resin with the following structure (Mw 18,000, acid value 82 mgKOH / g)

[0587] [Chemical Formula 45]

[0588]

[0589] C2-H1: Resin with the following structure (Mw 8,500, acid value 82 mgKOH / g)

[0590] [Chemical Formula 46]

[0591]

[0592] C2-H2: Resin with the following structure (the values ​​indicated on the main chain are molar ratios. Mw: 10,500, amine value: 105 mgKOH / g)

[0593] [Chemical Formula 47]

[0594]

[0595] <Solvent>

[0596] S-1: Propylene glycol monomethyl ether acetate (PGMEA)

[0597] S-2: Propylene glycol monomethyl ether (PGME)

[0598] S-3: Cyclohexanone

[0599] S-4: 3-Methoxybutanol

[0600] <Resin>

[0601] B-1: Resin with the following structure (the values ​​indicated on the main chain are molar ratios. Mw: 11,000, acid value: 69 mgKOH / g)

[0602] [Chemical Formula 48]

[0603]

[0604] B-2: Resin with the following structure (the values ​​indicated on the main chain are molar ratios. Mw 21,000, double bond equivalent 470)

[0605] [Chemical Formula 49]

[0606]

[0607] B-3: Resin with the following structure (the values ​​indicated on the main chain are molar ratios. Mw: 12,000, acid value: 80 mgKOH / g)

[0608] [Chemical Formula 50]

[0609]

[0610] <Radical Curable Compound (C1) Having a Molecular Weight of Less than 3,000>

[0611] C1-1 to C1-5: Compounds of the following structures

[0612] [Chemical Formula 51]

[0613]

[0614] <Comparative Compounds>

[0615] CA-1~CA-2: Compounds with the following structures

[0616] [Chemical Formula 52]

[0617]

[0618] <Thiol Compounds>

[0619] T-1 to T-4: compounds with the following structures

[0620] [Chemical Formula 53]

[0621]

[0622] <Evaluation>

[0623] (1) Evaluation of sensitivity

[0624] Each of the curable compositions obtained above was applied to an 8-inch (203.2 mm) silicon wafer with a primer layer by spin coating so that the film thickness after coating was 0.4 μm. The composition layer was then heated at 100°C for 2 minutes using a hot plate to form a composition layer. Next, the obtained composition layer was exposed to light at an illumination of 25,000 W / m² using a KrF ray scanning exposure machine through a mask having a 0.5 μm square pattern. 2 , pulse width 30 nanoseconds, frequency 40kHz, exposure 20mJ / cm 2 ~300mJ / cm 2 The exposed composition layer was exposed to light (KrF radiation) with a wavelength of 248 nm, varying the wavelength within a range of 100 nm. Next, the exposed composition layer was spray-developed at 23°C for 60 seconds using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) as a developer. Subsequently, the layer was rinsed with pure water using a rotary spray to form pixels.

[0625] The obtained pixels were observed at a magnification of 20,000 times using a scanning electron microscope (S-4800H, manufactured by Hitachi High-Tech Corporation).

[0626] The exposure dose required to achieve a pattern line width of 0.7 μm in the observed pixel was calculated, and the exposure sensitivity was evaluated according to the following criteria.

[0627] -Sensitivity Evaluation Criteria-

[0628] A: Exposure is 30mJ / cm 2 the following.

[0629] B: Exposure exceeds 30mJ / cm 2 and 50mJ / cm 2 the following.

[0630] C: Exposure exceeds 50mJ / cm 2 and 100mJ / cm 2 the following.

[0631] D: Exposure exceeds 100mJ / cm 2 and 200mJ / cm 2 the following.

[0632] E: Exposure exceeds 200mJ / cm 2 .

[0633] (2) Evaluation of rectangularity

[0634] In the pixel obtained as described above, the cut was performed at 100 mJ / cm 2 The patterned silicon wafer of the portion exposed with an exposure dose of 100 nm was observed with a scanning electron microscope (SEM) at a magnification of 20,000 times, and rectangularity was evaluated according to the following criteria.

[0635] -Evaluation criteria for rectangularity-

[0636] A: The width of the lower portion of the pattern in contact with the silicon wafer is within a range of 95% to 105% of the width of the upper portion of the pattern.

[0637] B: The width of the lower portion of the pattern in contact with the silicon wafer is 90% or more and less than 95% or exceeds 105% and is 110% or less relative to the width of the upper portion of the pattern.

[0638] C: The width of the lower portion of the pattern in contact with the silicon wafer is 85% or more and less than 90% or more than 110% and less than 115% of the width of the upper portion of the pattern.

[0639] D: The width of the lower portion of the pattern in contact with the silicon wafer is 80% or more and less than 85% or more than 115% and less than 120% of the width of the upper portion of the pattern.

[0640] E: The width of the lower portion in contact with the silicon wafer is less than 80% or greater than 120% of the width of the upper portion of the pattern.

[0641] (3) Evaluation of degassing

[0642] Each curable composition was applied on a silicon wafer using a spin coater, and then heated at 100° C. for 120 seconds using a hot plate (pre-baking) to obtain a coating film with a thickness of 1.0 μm.

[0643] Next, an i-line stepper exposure apparatus FPA-3000iS+ (manufactured by Canon Inc.) was used to expose the film at 400 mJ / cm through a mask having a 0.8 μm checkerboard pattern. 2 The exposure was performed with an exposure dose of . Next, outgassing was collected in a vacuum clean oven at 100°C for 1 hour, and the outgassing amount was calculated based on the peaks obtained by gas chromatography-mass spectrometry (GC / MS). The obtained outgassing amount was evaluated according to the following criteria.

[0644] -Evaluation criteria for degassing-

[0645] A: The outgassing amount is less than 0.01ppm.

[0646] B: The outgassing amount is 0.01 ppm or more and less than 0.05 ppm.

[0647] C: The outgassing amount is 0.05 ppm or more and less than 0.10 ppm.

[0648] D: The outgassing amount is 0.10 ppm or more and less than 1 ppm.

[0649] E: The outgassing amount is 1 ppm or more.

[0650] (4) Evaluation of coating unevenness

[0651] Each curable composition was applied to a silicon wafer using a spin coater and then heated (prebaked) at 100°C for 120 seconds using a hot plate to obtain a 1.0 μm thick coating film. The number of streaks in the coating film was visually counted. The number of streaks was used to evaluate coating unevenness according to the following criteria.

[0652] -Evaluation criteria for uneven coating-

[0653] A: The number of uneven stripes is 0.

[0654] B: 1 to 2 uneven strips.

[0655] C: 3 to 5 uneven strips.

[0656] D: There are 6 to 10 uneven strips.

[0657] E: There are 11 or more stripe-shaped unevennesses.

[0658] The evaluation results are summarized in Tables 8 to 10.

[0659] [Table 8]

[0660]

[0661] [Table 9]

[0662]

[0663] [Table 10]

[0664]

[0665] As shown in Tables 8 to 10 above, the curable compositions of Examples were superior in sensitivity to the curable compositions of Comparative Examples.

[0666] Furthermore, as shown in Tables 8 to 10 above, the curable compositions of Examples were also excellent in rectangularity, degassing suppression, and coating unevenness suppression.

[0667] (Example 101: Fabrication of a Solid-State Imaging Element)

[0668] The curable composition of Example 1 was applied to a silicon wafer by spin coating to a film thickness of 0.4 μm. The film was then heated at 100°C for 2 minutes using a hot plate. An i-ray stepper FPA-3000i5+ (manufactured by Canon Inc.) was then used at a rate of 1,000 mJ / cm 2 , exposed through a mask with a 1.0 μm square dot pattern. Then, using a 0.3% by mass aqueous solution of tetramethylammonium hydroxide (TMAH), spin-on immersion development was performed at 23°C for 60 seconds. Then, it was rinsed by rotary spraying and then washed with pure water. Next, using a hot plate, heating at 200°C for 5 minutes, a red pattern formed by curing the curable composition of Example 1 was formed on the silicon wafer. Similarly, the curable composition of Example 61 (green) and the curable composition of Example 31 (blue) were patterned in sequence to form red, green and blue colored patterns (Bayer patterns).

[0669] In addition, as disclosed in US Pat. No. 3,971,065, the Bayer pattern refers to a pattern in which a 2×2 array of color filter elements having one red element, two green elements, and one blue element is repeated.

[0670] The obtained color filter was assembled into a solid-state imaging element according to a known method. It was confirmed that when any of the curable compositions prepared in the examples was used, the solid-state imaging element had excellent adhesion in the cured film, and a solid-state imaging element with excellent image recognition performance was obtained.

[0671] The entire contents of Japanese Patent Application No. 2023-021859 filed on February 15, 2023 and Japanese Patent Application No. 2023-193207 filed on November 13, 2023 are incorporated herein by reference.

[0672] All documents, Japanese patent applications, and technical standards described in this specification are incorporated herein by reference to the same extent as if each individual document, Japanese patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A curable composition comprising: Compounds in which an indole skeleton is directly linked to an oxime group or a ketoxime group; Free radical curable compounds; and Resin, The resin includes a resin having a graft chain and a crosslinking group.

2. The curable composition according to claim 1, wherein The compound in which the indole skeleton is directly linked to an oxime group or a ketoxime group is a compound represented by the following formula (1): In formula (1), R1 represents an alkyl group, an aryl group, a heteroaryl group, an alkoxy group, an aryloxy group or a heteroaryloxy 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 or a monovalent organic group, Ar represents an aryl group or a heteroaryl group, and n represents 0 or 1.

3. The curable composition according to claim 2, wherein The Ar in the formula (1) is a group represented by the following formula (2), In formula (2), Ar1 and Ar2 each independently represent an arylene group or a heteroarylene group, and R 21 Each independently represents a halogen atom or a monovalent organic group, m represents an integer of 0 to 5, and * represents a bonding portion to the nitrogen atom of the indole ring.

4. The curable composition according to claim 1 or 2, wherein The compound in which the indole skeleton is directly linked to an oxime group or a ketoxime group is a mixture of a compound having one oxime group or a ketoxime group in one molecule and a compound having two or more oxime groups or a ketoxime group in one molecule. The curable composition according to claim 1 or 2, further comprising a polyfunctional thiol compound.

6. The curable composition according to claim 1 or 2, wherein The resin having graft chains and crosslinking groups is an acrylic resin.

7. The curable composition according to claim 1 or 2, wherein The resin having a graft chain and a crosslinkable group further has at least one group selected from the group consisting of a carboxylic acid group, a sulfonic acid group, and a phosphoric acid group.

8. The curable composition according to claim 1 or 2, wherein The crosslinkable group is at least one group selected from the group consisting of an ethylenically unsaturated group and a cyclic ether group.

9. The curable composition according to claim 1 or 2, wherein The content of the radical-curable compound having a molecular weight of less than 3000 in the radical-curable compound is less than 15% by mass based on the total solid content.

10. The curable composition according to claim 9, wherein When the mass of the radical curable compound having a molecular weight of less than 3000 is defined as W1 and the mass of the compound in which the indole skeleton is directly linked to an oxime group or a ketoxime group is defined as W2, W1 / W2<5 is satisfied. 11 . The curable composition according to claim 1 , further comprising a colorant. 12 . A method for producing a cured product, comprising irradiating the curable composition according to claim 1 or 2 with an excimer laser having a wavelength of 150 nm to 300 nm.

13. A film formed by curing the curable composition according to claim 1 or 2. An optical element comprising the film according to claim 13 .

15. An image sensor comprising the film according to claim 13. A solid-state imaging element comprising the film according to claim 13 . 17 . An image display device comprising the film according to claim 13 .

Images