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

Abstract

To provide a composition capable of forming a film which offers superior infrared shieldability, light resistance, heat resistance, moisture resistance and less defects.SOLUTION: A composition containing a near-infrared absorbing compound (A) and a resin (B) is provided, the near-infrared absorbing compound (A) containing a compound (A1) represented by a general formula below and a compound (A2) other than the compound (A1), both compounds having different maximum absorption wavelengths.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a composition containing a near-infrared absorbing compound. [Background technology]

[0002] Video cameras, digital cameras, and smartphones use solid-state image sensors (CCDs) and CMOSs ​​(complementary metal-oxide-semiconductors) to produce color images. Since the light-receiving section of these solid-state image sensors uses silicon photodiodes, which are sensitive to infrared light, it is necessary to perform luminous sensitivity correction, and an optical filter is placed to block infrared light. Such optical filters are manufactured, for example, using a composition containing a near-infrared absorbing dye.

[0003] For example, Patent Document 1 discloses a curable resin composition containing a dye having a maximum absorption wavelength in the range of 600 to 850 nm. Patent Document 2 also discloses a near-infrared absorption composition containing at least two cyanine compounds with different maximum absorption wavelengths. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2014-130343 [Patent Document 2] Japanese Patent Publication No. 2009-185161 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] Optical filters designed to block infrared radiation are required to block infrared radiation across a wide wavelength range. Furthermore, because such filters are used in various environments, high durability (high light resistance, heat resistance, and moisture resistance) is essential. Additionally, defects within the optical filter affect its infrared blocking capabilities, therefore, the generation of foreign matter and other defects must be suppressed.

[0006] The present invention aims to provide a composition that has excellent infrared shielding properties, high light resistance, heat resistance, and moisture resistance, and can form a film with few defects. [Means for solving the problem]

[0007] The present invention relates to a composition comprising a near-infrared absorbing compound (A) and a resin (B), The near-infrared absorbing compound (A) relates to a composition comprising a compound (A1) represented by general formula (1) and a compound (A2) other than compound (A1), each having different maximum absorption wavelengths. General formula (1) [ka]

[0008] In general formula (1), X1~X8, Y l ~Y8 independently represent a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group. Furthermore, X1~X8 may independently bond to each other to form an optionally substituted aromatic ring. However, one or more of X1 and X2, X3 and X4, X5 and X6, and X7 and X8 may bond to each other to form an optionally substituted aromatic ring. Z represents a ligand having one or more coordination sites for an Al atom. [Effects of the Invention]

[0009] According to the present invention described above, it is possible to provide a composition that can form a film with excellent infrared shielding properties, high light resistance, heat resistance, and moisture resistance, and with few defects. Furthermore, the present invention can provide a film, an optical filter, an image display device, a solid-state image sensor, and an infrared sensor. [Brief explanation of the drawing]

[0010] [Figure 1] Figure 1 shows a schematic cross-sectional view of an infrared sensor equipped with the film of the present invention. [Modes for carrying out the invention]

[0011] The embodiments for carrying out the composition of the present invention will be described in detail below. However, the present invention is not limited to the following embodiments and can be modified and implemented within the scope of solving the problem.

[0012] In this specification, unless otherwise specified, "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" means "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. Also, "CI" means Color Index (CI; issued by The Society of Dyers and Colourists). A polymerizable unsaturated group is an ethylenically unsaturated double bond. Regarding the molecular weight of the compounds in this invention, for low molecular weight compounds whose molecular weight can be specified, the molecular weight is calculated by formula weight or measured by ESI-MS (electrospray ionization mass spectrometry), while for compounds with a molecular weight distribution, the weight-average molecular weight in polystyrene terms is measured by gel permeation chromatography using tetrahydrofuran as the solvent. A monomer is a compound that forms a resin through polymerization. A monomer is in an unreacted state, while a monomer unit is the state in which the monomer has polymerized and formed a resin.

[0013] <Composition> The composition of the present invention comprises a near-infrared absorbing compound (A) and a resin (B). The near-infrared absorbing compound (A) is characterized by comprising a compound (A1) represented by general formula (1) and a compound (A2) other than compound (A1), each having different maximum absorption wavelengths. General formula (1) [ka]

[0014] In general formula (1), X1~X8, Y l ~Y8 independently represent a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group. Furthermore, X1~X8 may independently bond to each other to form an optionally substituted aromatic ring. However, one or more of X1 and X2, X3 and X4, X5 and X6, and X7 and X8 may bond to each other to form an optionally substituted aromatic ring. Z represents a ligand having one or more coordination sites for an Al atom.

[0015] The mechanism by which the above-described composition can solve the problems of the present invention is not clear, but we speculate as follows.

[0016] By using a compound (A1) represented by general formula (1) and a compound (A2) other than compound (A1) as near-infrared absorbing compounds, which have maximum absorption wavelengths in different wavelength ranges, the absorption spectrum waveform of the film is broadened compared to using a single near-infrared absorbing compound, allowing for the blocking of infrared radiation across a wide wavelength range. Furthermore, because compound (A1) represented by general formula (1) has excellent heat resistance, light resistance, and moisture resistance, a film with superior resistance can be obtained even if compound (A2) other than compound (A1) has poor resistance. This is presumed to be because the energy absorbed by compound (A2) other than compound (A1) is transferred to the side of compound (A1) represented by general formula (1), which has superior resistance, thereby suppressing the decomposition of compound (A2) other than compound (A1). Furthermore, although compound (A1) represented by general formula (1) is difficult to disperse, the dispersion stability is improved and the generation of foreign matter is suppressed by using compound (A2) other than compound (A1) represented by general formula (1) in combination. This is presumed to be because aggregation is suppressed by the adsorption or orientation of compound (A2) other than compound (A1) represented by general formula (1) onto compound (A1).

[0017] The components included in or potentially included in the composition of one embodiment will be described in detail below.

[0018] [Near-infrared absorbing compound (A)] The composition of the present invention includes, as near-infrared absorbing compound (A), a compound (A1) represented by general formula (1) and a compound (A2) other than compound (A1), which have different maximum absorption wavelengths. Near-infrared absorbing compound (A) is a compound having maximum absorption at a wavelength of 700 to 2,000 nm.

[0019] (Compound (A1) represented by general formula (1)) Compound (A1) represented by general formula (1) is as follows:

[0020] General formula (1) [ka]

[0021] In general formula (1), X1~X8, Y l ~Y8 independently represent a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxy group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group. Furthermore, X1~X8 may independently bond to each other to form an optionally substituted aromatic ring. However, one or more of X1 and X2, X3 and X4, X5 and X6, and X7 and X8 may bond to each other to form an optionally substituted aromatic ring. Z represents a ligand having one or more coordination sites for an Al atom.

[0022] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0023] Examples of alkyl groups that may have substituents include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl, n-octyl, stearyl, and 2-ethylhexyl groups. Examples of alkyl groups with substituents include trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, and 2,4-dichlorobenzyl groups.

[0024] Examples of the "aryl group" which may have substituents include a phenyl group, a naphthyl group, anthuryl group, and the like. Examples of "substituted aryl groups" include p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, and 2-aminoanthraquinonyl group.

[0025] Examples of "cycloalkyl groups" that may have substituents include cyclopentyl groups, cyclohexyl groups, adamantyl groups, and the like. Examples of "substituted cycloalkyl groups" include the 2,5-dimethylcyclopentyl group and the 4-tert-butylcyclohexyl group.

[0026] Examples of heterocyclic groups that may have substituents include pyridyl, pyrazyl, piperidino, pyranyl, morpholino, and acridinyl groups. Examples of heterocyclic groups with substituents include 3-methylpyridyl, N-methylpiperidyl, and N-methylpyrrolyl groups.

[0027] Examples of alkoxyl groups that may have substituents include linear or branched alkoxyl groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, neopentyloxy, 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy. Examples of "substituted alkoxyl groups" include trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2-ditrifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, and benzyloxy groups.

[0028] Examples of aryloxy groups that may have substituents include phenoxy groups, naphthoxy groups, anthuryloxy groups, and so on. Examples of "substituted aryloxy groups" include p-methylphenoxy group, p-nitrophenoxy group, p-methoxyphenoxy group, 2,4-dichlorophenoxy group, pentafluorophenoxy group, and 2-methyl-4-chlorophenoxy group.

[0029] Examples of alkylthio groups that may have substituents include methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, octylthio, decylthio, dodecylthio, and octadecylthio groups. Examples of "alkylthio groups having substituents" include methoxyethylthio groups, aminoethylthio groups, benzylaminoethylthio groups, methylcarbonylaminoethylthio groups, and phenylcarbonylaminoethylthio groups.

[0030] Examples of the arylthio group which may have substituents include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 9-anthrylthio group, and the like. Examples of "substituted arylthio groups" include chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nitrophenylthio group, 2-aminophenylthio group, and 2-hydroxyphenylthio group.

[0031] Examples of substituents on the aromatic ring that may have substituents include halogen atoms, nitro groups, nitrile groups, carboxyl groups, sulfone groups, alkyl groups that may have substituents, aryl groups that may have substituents, cycloalkyl groups that may have substituents, alkoxyl groups that may have substituents, aryloxy groups that may have substituents, alkylthio groups that may have substituents, and arylthio groups that may have substituents.

[0032] The ligand represented by Z may be a ligand having one or more coordination sites selected from those that coordinate anionically to the Al atom and those that coordinate with the Al atom using a lone pair of electrons. The anionally coordinating site may be dissociated or non-dissociated. The ligand may have one coordination site for the Al atom, or it may have two or more coordination sites for the Al atom.

[0033] Examples of Z include halogen atoms, hydroxyl groups, optionally substituted alkoxy groups, optionally substituted aryloxy groups, optionally substituted alkylthio groups, and optionally substituted arylthio groups. Among these, from the viewpoint of suppressing foreign matter, a ligand having a phosphorus atom is preferred. Furthermore, Z is preferably a ligand having a hydrophobic group from the viewpoint of heat resistance and moisture resistance, and more preferably a ligand having a phosphorus atom and a hydrophobic group. The hydrophobic group described above represents a group with low affinity for water. Examples of groups with low affinity for water include alkyl groups (which may have substituents), aryl groups (which may have substituents), alkoxy groups (which may have substituents), and aryloxy groups (which may have substituents). The number of carbon atoms in alkyl and alkoxy groups is preferably 1 to 30. The number of carbon atoms in aryl and aryloxy groups is preferably 6 to 30. Examples of substituents include halogen atoms, nitro groups, and nitrile groups.

[0034] Ligands containing a phosphorus atom include, for example, the ligand represented by the following general formula (2).

[0035] General formula (2) [Chemical formula]

[0036] In general formula (2), R 29 and R 30 each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, an alkoxyl group which may have a substituent or an aryloxy group which may have a substituent. * represents a bond with Al.

[0037] Examples of the "alkyl group" of the alkyl group which may have a substituent, the "aryl group" of the aryl group which may have a substituent, the "alkoxyl group" of the alkoxyl group which may have a substituent, and the "aryloxy group" of the aryloxy group which may have a substituent are the same as those exemplified in the description of the above general formula (1).

[0038] From the viewpoints of heat resistance and moisture resistance, general formula (2) preferably has at least one of R 29 and R 30 being an aryl group which may have a substituent or an aryloxy group which may have a substituent. More preferably, both R 29 and R 30 are aryl groups or aryloxy groups. Particularly preferably, both R 29 and R 30 are phenyl groups or phenoxy groups.

[0039] Specific examples of the compound (A1) represented by general formula (1) are shown below. However, the present invention is not limited thereto.

[0040] [Chemical formula] [Chemical formula]

[0041] The compound (A1) represented by general formula (1) preferably contains compounds in which two or more of X1 and X2, X3 and X4, X5 and X6, and X7 and X8 are bonded to each other to form an aromatic ring which may have substituents, and more preferably contains compounds in which three or more are bonded to each other to form an aromatic ring which may have substituents, from the viewpoint of infrared shielding, light resistance, and heat resistance.

[0042] The compound (A1) represented by general formula (1) preferably contains two or more compounds with different molecular structures. This helps to further suppress foreign substances. Furthermore, it is more preferable that the compound (A1) represented by general formula (1) contains 30% by mass or more of compounds in which three or more of X1 and X2, X3 and X4, X5 and X6, and X7 and X8 are bonded to each other to form an aromatic ring which may have substituents.

[0043] The content of compound (A1) represented by general formula (1) is preferably 30% by mass or more, more preferably 30-95% by mass, and even more preferably 40-80% by mass, of 100% by mass of near-infrared absorbing compound (A), from the viewpoint of infrared blocking, light resistance, heat resistance, moisture resistance, and foreign matter suppression.

[0044] (Compounds other than compound (A1) represented by general formula (1) (A2)) Compound (A2) other than compound (A1) represented by general formula (1) (hereinafter also simply referred to as compound (A2)) is not particularly limited as long as it has infrared blocking ability and its maximum absorption wavelength is in a different wavelength range than compound (A1) represented by general formula (1), and any known compound can be used.

[0045] Examples of compound (A2) include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, indigo compounds, immonium compounds, anthraquinone compounds, pyrrolopyrrole compounds, squarylium compounds, crokonium compounds, rylene compounds, oxonol compounds, pyromethene compounds, and azomethine compounds. Among these, from the viewpoint of light resistance and heat resistance, it is preferable to include at least one selected from the group consisting of squarylium compounds, naphthalocyanine compounds, cyanine compounds, pyrrolopyrrole compounds, indigo compounds, phthalocyanine compounds, and crokonium compounds, with squarylium compounds, naphthalocyanine compounds, pyrrolopyrrole compounds, indigo compounds, phthalocyanine compounds, and crokonium compounds being more preferable, and naphthalocyanine compounds and indigo compounds being particularly preferred.

[0046] Cyanine compounds are described in International Publication No. 2006 / 006573, Japanese Patent Publication No. 2009-108267, International Publication No. 2010 / 073857, Japanese Patent Publication No. 2013-241598, Japanese Patent Publication No. 2016-113501, Japanese Patent Publication No. 2016-113504, Japanese Patent Publication No. 2017-031394, etc.; Phthalocyanine compounds are described in Japanese Patent Publication No. Hei 4-23868, Japanese Patent Publication No. Hei 06-192584, Japanese Patent Publication No. 2000-63691, International Publication No. 2014 / 208 514, etc.; Naphthalocyanine compounds are described in JP-A-11-152414, JP-A-2000-86919, JP-A-2009-29955, JP-A-2016-053617, International Publication No. 2017 / 002920, International Publication No. 2018 / 186490, etc.; Indigo compounds are described in JP-A-2013-230412, etc.; Immonium compounds are described in JP-A-2005-336150, JP-A-2007-197492, JP-A-2008-88 Japanese Patent Publication No. 426, etc.; Anthraquinone compounds: Japanese Patent Publication No. S62-903, Japanese Patent Publication No. H1-172458, etc.; Pyrrolopyrrole compounds: Japanese Patent Publication No. 2009-263614, Japanese Patent Publication No. 2010-90313, Japanese Patent Publication No. 2011-068731; Squallium compounds: Japanese Patent Publication No. 2011-132361, Japanese Patent Publication No. 2016-142891, International Publication No. 2017 / 135359, International Publication No. 2018 / 225837, Japanese Patent Publication No. 2019-00 Examples of compounds described include those in Japanese Patent Publication No. 1987, International Publication No. 2020 / 054718, Japanese Patent Publication No. 2020-172614, International Publication No. 2021 / 029195, etc.; Croconium compounds are described in International Publication No. 2017-146187, International Publication No. 2019 / 021767, etc.; Pyrometen compounds are described in Japanese Patent Publication No. 2018-123093, Japanese Patent Publication No. 2019-077673, Japanese Patent Publication No. 2020-189933, International Publication No. 2020 / 162345, etc.

[0047] [Squallium compounds] The squarylium compound is not particularly limited, and any known compound can be used. For example, a compound represented by the following general formula (3) can be used.

[0048] General formula (3) [ka]

[0049] In general formula (3), X1 and X2 each independently represent an aryl group, a heterocyclic group, or a group represented by the following general formula (4).

[0050] General formula (4) [ka]

[0051] In general formula (4), X3 represents a heterocyclic group, Y1 to Y3 each independently represent a hydrogen atom or an alkyl group, and n1 represents an integer of 0 or more. Y1 and Y2, Y1 and X3, and Y2 and Y3 may each bond to each other to form a ring, and if n1 is 2 or more, multiple Y2 and Y3 may be the same or different. * represents a bond.

[0052] The number of carbon atoms in the aryl groups represented by X1 and X2 is preferably 6 to 48, more preferably 6 to 22, and particularly preferably 6 to 12.

[0053] The heterocyclic groups represented by X1 to X3 are preferably 5-membered or 6-membered heterocyclic groups. Furthermore, the heterocyclic groups are preferably monocyclic heterocyclic groups or fused heterocyclic groups with 2 to 8 fusion numbers, more preferably monocyclic heterocyclic groups or fused heterocyclic groups with 2 to 4 fusion numbers, and particularly preferably monocyclic heterocyclic groups or fused heterocyclic groups with 2 fusion numbers. The heteroatoms constituting the ring of the heterocyclic group include nitrogen atoms, oxygen atoms, and sulfur atoms, with nitrogen atoms being preferred. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3, and more preferably 1 or 2.

[0054] The number of carbon atoms in the alkyl group represented by Y1 to Y3 is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 8. The alkyl group may be linear, branched, or cyclic.

[0055] n1 is preferably an integer between 0 and 2, and more preferably 0 or 1.

[0056] When Y1 and Y2, Y1 and X3, and Y2 and Y3 each form a ring with each other, the preferred linking group is a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, alkylene groups having 1 to 10 carbon atoms, and combinations thereof. The alkylene group may be unsubstituted or may have substituents. An example of a substituent is substituent W, which will be described later.

[0057] The groups represented by X1 and X2 preferably have substituents. Examples of substituents include substituent W, which will be described later.

[0058] {substituent W} The substituent W can be a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, or -OR 1 , -COR 1 ,-COOR 1 , -OCOR 1 , -NR 1 R 2 , -NHCOR 1 ,-CONR 1 R 2 ,-NHCONR 1 R 2 , -NHCOOR 1 , -SR 1 , -SO2R 1 , -SO2R 1 , -NHSO2R 1 or -SO2NR 1 R 2 Examples include R. 1 and R 2 Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. 1 and R 2 They may combine to form a ring. Note that -COOR 1 and -SO2OR 1 R 1 In the case of hydrogen, the hydrogen atom may dissociate, or it may exist in a salt state.

[0059] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, with linear or branched being preferred. The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8. The alkenyl group may be linear, branched, or cyclic, with linear or branched being preferred. The number of carbon atoms in the alkynyl group is preferably 2 to 40, more preferably 2 to 30, and particularly preferably 2 to 25. The alkynyl group may be linear, branched, or cyclic, with linear or branched being preferred. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and particularly preferably 6 to 12. The heteroaryl group is preferably a monocyclic heteroaryl group or a fused ring heteroaryl group with 2 to 8 condensation rings, and more preferably a monocyclic heteroaryl group or a fused ring heteroaryl group with 2 to 4 condensation rings. The heteroatoms constituting the ring of the heteroaryl group are preferably nitrogen atoms, oxygen atoms, or sulfur atoms. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and particularly preferably 3 to 12. The alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group may have substituents or be unsubstituted. Examples of substituents include the substituent W mentioned above.

[0060] Furthermore, in general formula (3), the cation exists in a delocalized state as follows.

[0061] [ka]

[0062] Furthermore, squarylium compounds include, for example, compounds represented by the following general formulas (5) to (9).

[0063] General formula (5) [ka]

[0064] In general formula (5), Y 11 and Y 12 Each of these independently represents a hydrogen atom or a substituent. 13 and Y 14 Each of these independently represents a substituent. 11 and n 12 Each of these independently represents an integer from 0 to 3, and n 11 If it is 2 or more, two Y 13 They may also bond together to form a ring, n 12 If it is 2 or more, two Y 14 They may join together to form a ring. 21 ~Y 24 Each of these independently represents an alkyl group, an aryl group, or a heteroaryl group, Y 21 and Y 22 , Y 23 and Y 24 , Y 21 and Y 13 , Y 22 and Y 13 , Y 23 and Y 14 , Y 24 and Y 14 , Y 21 and two Y 13 A ring is formed when two elements bond together, Y 23 and two Y 14 The rings formed by the bonding of elements may bond to each other to form further rings.

[0065] Y 11 and Y 12 The substituent represented by is preferably a group having an active hydrogen group, such as -OH, -SH, -COOH, -SO3H, -NR 3 R 4 , -NHCOR 3 ,-CONR 3 R 4 ,-NHCONR 3R 4 、 -NHCOOR 3 、 -NHSO2R 3 、 -B(OH)2 and -PO(OH) 2 are more preferable, and -OH, -SH and -NR 3 R 4 are particularly preferable. R 3 and R 4 each independently represent a hydrogen atom or a substituent. R 3 and R 4 Examples of the substituent represented by include an alkyl group, an aryl group or a heteroaryl group, and an alkyl group is preferable.

[0066] Y 13 and Y 14 Examples of the substituent represented by include the above-described substituent W.

[0067] Y 21 ~ Y 24 The number of carbon atoms of the alkyl group represented by is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 8. The alkyl group may be linear, branched or cyclic, and linear or branched is preferable. Y 21 ~ Y 24 The number of carbon atoms of the aryl group represented by is preferably 6 to 30, more preferably 6 to 20, and particularly preferably 6 to 12. Y 21 ~ Y 24 The heteroaryl group represented by is preferably a monocyclic heteroaryl group or a condensed-ring heteroaryl group with 2 to 8 condensations, and more preferably a monocyclic heteroaryl group or a condensed-ring heteroaryl group with 2 to 4 condensations. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the ring of the heteroaryl group are preferably nitrogen atoms, oxygen atoms or sulfur atoms. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and particularly preferably 3 to 12. The alkyl group, aryl group and heteroaryl group may have a substituent or may be unsubstituted. Examples of the substituent include the above-described substituent W.

[0068] n 11 and n 12 each preferably independently represents an integer of 0 to 2. When n 11 is 2 or more, two Ys 13 may combine with each other to form a ring. When n 12 is 2 or more, two Ys 14 may combine with each other to form a ring. When forming a ring, examples of the linking group include divalent linking groups selected from the group consisting of -CO-, -O-, -NH-, alkylene groups having 1 to 10 carbon atoms, and combinations thereof. The alkylene group as the linking group may have a substituent or may be unsubstituted. Examples of the substituent include the above-described substituent W.

[0069] Y 21 and Y 22 Y 23 and Y 24 Y 21 and Y 13 Y 22 and Y 13 Y 23 and Y 14 Y 24 and Y 14 may combine with each other to form a ring. Also, when two Ys 13 combine with each other to form a ring, Y 21 and the ring formed by the combination of two Ys 13 may combine with each other to further form a ring. Also, when two Ys 14 combine with each other to form a ring, Y 23 and the ring formed by the combination of two Ys 14 may combine with each other to further form a ring. When forming a ring, examples of the linking group include divalent linking groups selected from the group consisting of -CO-, -O-, -NH-, alkylene groups having 1 to 10 carbon atoms, and combinations thereof. The alkylene group as the linking group may have a substituent or may be unsubstituted. Examples of the substituent include the above-described substituent W.

[0070] General formula (6) [ka]

[0071] In general formula (6), Y 31 ~Y 38 Each of these independently represents a hydrogen atom or an alkyl group. 31 and Y 32 , Y 31 and Y 34 , Y 32 and Y 33 , Y 35 and Y 36 , Y 35 and Y 38 , Y 36 and Y 38 These may be joined together to form a ring. 41 and Y 42 Each of these independently represents a hydrogen atom or a substituent. 43 and Y 44 Each of these independently represents a substituent. 21 and n 22 Each of these independently represents an integer from 0 to 3, and n 21 If it is 2 or more, two Y 43 They may also bond together to form a ring, n 22 If it is 2 or more, two Y 44 They may join together to form a ring.

[0072] Y 31 ~Y 38 The number of carbon atoms in the alkyl group represented by is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, with linear or branched being preferred. The alkyl group may have substituents or may be unsubstituted. Examples of substituents include the substituent W mentioned above.

[0073] Y 31 and Y 32 , Y 31 and Y 34 , Y 32 and Y 33 , Y 35 and Y 36 , Y 35 and Y38 , Y 36 and Y 38 These may bond to each other to form a ring. When a ring is formed, the linking group may be a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, alkylene groups having 1 to 10 carbon atoms, and combinations thereof. The alkylene group as a linking group may have substituents or may be unsubstituted. An example of a substituent is the substituent W mentioned above.

[0074] n 21 and n 22 It is preferable that each of these independently represents an integer between 0 and 2. 21 If it is 2 or more, two Y 43 They may also bond together to form a ring, n 22 If it is 2 or more, two Y 44 The groups may bond together to form a ring. When a ring is formed, the linking group may be a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, alkylene groups having 1 to 10 carbon atoms, and combinations thereof. The alkylene group as a linking group may have substituents or may be unsubstituted. An example of a substituent is the substituent W mentioned above.

[0075] General formula (7) [ka]

[0076] In general formula (7), Y 51 and Y 52 Each of these independently represents a substituent. 53 ~Y 58 Each of these independently represents a hydrogen atom or a substituent. Z1 and Z2 independently represent a carbon atom, a boron atom, or C(=O). When Z1 is a carbon atom, n 33 It is 2, and in the case of a boron atom, n 33 It is 1, and in the case of C (=O), n 33 is 0, and if Z2 is a carbon atom, then n 34 It is 2, and in the case of a boron atom, n 34It is 1, and in the case of C (=O), n 34 n is 0. 33 If it is 2, then 2 Y 53 They may be the same or different, and the two Y 53 They may also bond together to form a ring, n 34 If it is 2, then 2 Y 54 They may be the same or different, and the two Y 54 They may join together to form a ring. 31 and n 32 Each of these independently represents an integer from 0 to 5, and n 31 If there are 2 or more, multiple Y 51 They may be the same or different, and there may be multiple Y 51 Two of the Y 51 They may also bond together to form a ring, n 32 If there are 2 or more, multiple Y 52 They may be the same or different, and there may be multiple Y 52 Two of the Y 52 These elements may bond together to form a ring. Q represents an aryl group or a heteroaryl group, and m represents an integer from 0 to 2. Examples of substituents include the substituent W mentioned above.

[0077] General formula (8) [ka]

[0078] In general formula (8), X 61 ~X 64 These are, independently, a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, an aralkyl group, and an -OR group. 50 , -COR 51 ,-COOR 52 , -OCOR 53 , -NR 54 R 55 , -NHCOR 56 ,-CONR 57 R 58 ,-NHCONR 59 R60 , -NHCOOR 61 , -SR 62 , -SO2R 63 , -SO2OR 64 , -NHSO2R 65 or -SO2NR 66 R 67 , -B(OR 68 )2 and -NHBR 69 R 70 Represents R 50 ~R 70 Each of these independently represents a hydrogen atom, an alkyl group which may have substituents, an alkenyl group, an alkynyl group, an aryl group, a heteroaryl group, and an aralkyl group. Note that -COOR 52 R 52 If it is hydrogen (i.e., a carboxyl group), the hydrogen atom may dissociate (i.e., a carbonate group), and it may be in the form of a salt. Also, -SO2OR 64 R 64 If is a hydrogen atom (i.e., a sulfo group), the hydrogen atom may dissociate (i.e., a sulfonate group), and may be in the form of a salt. Also, X 61 and X 62 , X 63 and X 64 They may also be joined together to form a ring. 61 ~Y 70 This consists of a hydrogen atom, an alkyl group, a sulfo group, and -SO3M 1 Or it represents a halogen atom. M 1 This represents an inorganic or organic cation.

[0079] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 12, and particularly preferably 1 to 8. The alkyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8. The alkenyl group may be linear, branched, or cyclic. The number of carbon atoms in the alkynyl group is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8. The alkynyl group may be linear, branched, or cyclic. The number of carbon atoms in the aryl group is preferably 6 to 25, more preferably 6 to 15, and particularly preferably 6 to 10. The alkyl portion of the aralkyl group is the same as that of the alkyl group described above. The aryl portion of the aralkyl group is the same as that of the aryl group described above. The number of carbon atoms in the aralkyl group is preferably 7 to 40, more preferably 7 to 30, and particularly preferably 7 to 25. The heteroaryl group is preferably a monocyclic or fused ring, more preferably a monocyclic or fused ring with 2 to 8 fused atoms, and particularly preferably a monocyclic or fused ring with 2 to 4 fused atoms. The number of heteroatoms constituting the ring of the heteroaryl group is preferably 1 to 3. The heteroatoms constituting the ring of the heteroaryl group are preferably nitrogen atoms, oxygen atoms, or sulfur atoms. The heteroaryl group is preferably a 5-membered or 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and particularly preferably 3 to 12. Alkyl groups, alkenyl groups, alkynyl groups, aryl groups, heteroaryl groups, and aralkyl groups may have substituents or may be unsubstituted. Examples of substituents include the substituent W mentioned above.

[0080] General formula (9) [ka]

[0081] In general formula (9), X7 and X8 each independently represent an arylene group, a heteroarylene group, or a group formed by combining two or more of these. 71 ~Y 76 and Y 81 ~Y 86 Each of these independently represents a hydrogen atom or a substituent, Y 71 ~Y 76 and Y 81 ~Y 86Two or more of these atoms may be bonded to each other to form a ring. Examples of substituents include the substituent W mentioned above.

[0082] The following are specific examples of squarylium compounds. However, the present invention is not limited to these examples.

[0083] [ka]

[0084] [ka]

[0085] [Naphthalocyanine compounds] The naphthalocyanine compound is not particularly limited, and any known compound can be used, except for compound (A1) represented by general formula (1). For example, a compound represented by the following general formula (10) can be used.

[0086] General formula (10) [ka]

[0087] In general formula (10), R 1 ~R 24 Each of these independently consists of a hydrogen atom, a halogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted heterocyclic group, and -OR 25 or -SR 26 Represents R 25 and R 26 Each of the following independently represents a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted aryl group. M represents two hydrogen atoms, a metal atom, a metal oxide, or a metal halogen. However, the metal is excluding Al.

[0088] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0089] R 1 ~R 24 The alkyl group, which may have substituents represented by , preferably has 1 to 20 carbon atoms, more preferably 1 to 12, and particularly preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, with linear or branched being preferred. Specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group, stearyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 3,5,5-trimethylhexyl group, cyclohexyl group, cyclopentyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclopentylmethyl group, and cyclopentylethyl group.

[0090] R 1 ~R 24 Examples of substituents on an alkyl group that may have substituents represented by include alkoxy groups, halogen groups, amino groups, cyano groups, nitro groups, and the like.

[0091] R 1 ~R 24 The aryl group, which may have substituents represented by , preferably has 6 to 30 carbon atoms, and more preferably 6 to 20. Specifically, examples include phenyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, biphenylyl group, etc.

[0092] R 1 ~R 24 Examples of substituents on an aryl group that may have substituents represented by include alkoxy groups, halogen groups, amino groups, cyano groups, nitro groups, and the like.

[0093] R 1 ~R 24The heterocyclic group which may have substituents represented by is preferably a 5-membered or 6-membered heterocyclic group. Specifically, examples include pyridyl group, pyrrolyl group, oxazolyl group, isoxazolyl group, thiazolyl group, isothiazolyl group, imidazolyl group, oxadiazolyl group, thiadiazolyl group, triazolyl group, tetrazolyl group, pyrazolyl group, pyrimidinyl group, pyridadinyl group, pyrazinyl group, triazinyl group, indolyl group, isoindolyl group, benzimidazolyl group, benzoxazolyl group, benzothiazolyl group, quinolyl group, carbazolyl group, and the like.

[0094] R 1 ~R 24 Examples of substituents on a heterocyclic group that may have substituents represented by include alkoxy groups, halogen groups, amino groups, cyano groups, nitro groups, and the like.

[0095] R 25 and R 26 The alkyl group which may have substituents represented by R 1 ~R 24 Examples include alkyl groups that may have substituents represented by .

[0096] R 25 and R 26 The aryl group which may have substituents represented by R 1 ~R 24 Examples include the same aryl group that may have substituents represented by .

[0097] When M represents two hydrogen atoms, the NMN portion in general formula (10) forms a structure represented as two NH groups. Examples of metal atoms represented by M include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, and tin. Examples of metal oxides represented by M include titanyl and vanadyl. Examples of metal halides represented by M include indium chloride, germanium chloride, tin(II) chloride, tin(IV) chloride, and silicon chloride. However, the metals represented by M in metal atoms, metal oxides, and metal halides exclude aluminum. Among these, M is preferably copper, zinc, cobalt, nickel, iron, vanadyl, titanyl, indium chloride, or tin(II) chloride, more preferably copper, zinc, vanadyl, or titanyl, and particularly preferably vanadyl.

[0098] The following are specific examples of naphthalocyanine compounds. However, the present invention is not limited to these.

[0099] [ka]

[0100] [Cyanine compounds] The cyanine compound is not particularly limited, and known compounds can be used. For example, a compound represented by the following general formula (11) can be used.

[0101] General formula (11) [ka]

[0102] In general formula (11), R1 to R5 each independently represent a hydrogen atom or a substituent, and any two of R1 to R5 may bond to form a ring. n represents an integer from 0 to 2, and in the case of 2, multiple R4s and R5s may be the same or different. Ar1 and Ar2 each independently represent an aryl group or a heterocyclic group. If the portion represented by X represents a cation, Y represents a counter anion, and m represents the number required to balance the charge. If the charge of the portion represented by X is 0, then m is 0.

[0103] The substituents represented by R1 to R5 include the substituent W mentioned above. When two of R1 to R5 bond to form a ring, the linking group is preferably a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, alkylene groups having 1 to 10 carbon atoms, and combinations thereof. The alkylene group as the linking group may be unsubstituted or may have substituents. The substituent W mentioned above is an example of a substituent.

[0104] n is preferably 0 or 1.

[0105] The number of carbon atoms in the aryl groups represented by Ar1 and Ar2 is preferably 6 to 48, more preferably 6 to 22, and particularly preferably 6 to 12. The heterocyclic groups represented by Ar1 and Ar2 are preferably 5-membered or 6-membered rings. Furthermore, the heterocyclic groups are preferably monocyclic or fused rings with 2 to 8 fusions, more preferably monocyclic or fused rings with 2 to 4 fusions, and particularly preferably monocyclic or fused rings with 2 fusions. Examples of heteroatoms constituting the ring of the heterocyclic group include nitrogen, oxygen, and sulfur atoms, with oxygen and sulfur atoms being preferred. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3, more preferably 1 or 2. The groups represented by Ar1 and Ar2 may have substituents. Examples of substituents include the substituent W mentioned above.

[0106] If the part represented by X represents a cation, then Y represents the counter anion, and m represents the number required to balance the charge. A counter anion is, for example, Cl - , Br - , I - p-toluenesulfonate ion, ethyl sulfate ion, PF6 - BF4 - ClO4 - Examples include tris(halogenoalkylsulfonyl)methide anion, di(halogenoalkylsulfonyl)imide anion, and tetracyanoborate anion. If the part represented by X indicates an anion, then Y represents the counter cation, and m represents the number required to balance the charge. A counter cation is, for example, Li. + na + , K + Mg 2+ Ca 2+ Ba 2+ Ag 2+ Fe 2+ Co 2+ Ni 2+ Cu 2+ Zn 2+ Examples include metal ions such as ammonium ions, triethylammonium ions, tributylammonium ions, pyridinium ions, tetrabutylammonium ions, guanidinium ions, tetramethylguanidinium ions, and diazobicycloundecenium. Note that if the charge of the part represented by X is 0, then Y does not exist (m is 0).

[0107] The following are specific examples of cyanine compounds. However, the present invention is not limited to these examples.

[0108] [ka]

[0109] [Pyrrolopyrrole compounds] The pyrrolopyrrole compound is not particularly limited, and known compounds can be used. For example, a compound represented by the following general formula (12) can be used.

[0110] General formula (12) [ka]

[0111] In general formula (12), R 1x and R 1y Each of these independently represents an alkyl group, an aryl group, or a heteroaryl group, and R 2 and R 3each independently represents a hydrogen atom or a substituent, R 2 and R 3 may be bonded to each other to form a ring, R 4 is a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, -BR 4x R 4y or a metal atom, and R 4 is R 1x , R 1y and R 3 and may be covalently or coordinately bonded to at least one selected from the group consisting of R 4x R 4y each independently represents a substituent. General formula (12) is described in, for example, JP-A-2009-263614, JP-A-2011-68731, and WO 2015 / 166873.

[0112] R 1x and R 1y are each independently preferably an aryl group or a heteroaryl group, more preferably an aryl group. Also, the alkyl group, aryl group, and heteroaryl group represented by R 1x and R 1y may have a substituent or may be unsubstituted. Examples of the substituent include an alkoxy group, a hydroxy group, a halogen atom, a cyano group, a nitro group, -OCOR 11 , -SOR 12 , -SO2R 13 and the like. R 11 ~R 13 each independently represents a hydrocarbon group or a heteroaryl group. Examples of the substituent also include the substituents described in paragraphs 0020 to 0022 of JP-A-2009-263614. Among them, preferred substituents include an alkoxy group, a hydroxy group, a halogen atom, a cyano group, a nitro group, -OCOR 11 , -SOR 12 , -SO2R 13 . The groups represented by R 1x and R 1y include an alkoxy group having a branched alkyl group, or -OCOR 11An aryl group having a group represented by as a substituent is preferred. The number of carbon atoms of the branched alkyl group is preferably 3 to 30, more preferably 3 to 20.

[0113] R 2 and R 3 at least one of them is preferably an electron-withdrawing group, R 2 represents an electron-withdrawing group, and R 3 more preferably represents a heteroaryl group. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. Also, the heteroaryl group is preferably a monocyclic or condensed ring, preferably a monocyclic or condensed ring with 2 to 8 condensed rings, more preferably a monocyclic or condensed ring with 2 to 4 condensed rings. The number of heteroatoms constituting the heteroaryl group is preferably 1 to 3, more preferably 1 to 2. The heteroatoms include, for example, nitrogen atoms, oxygen atoms, sulfur atoms. The heteroaryl group preferably has one or more nitrogen atoms. The two R 2 in the general formula (12) may be the same or different. Also, the two R 3 in the general formula (12) may be the same or different.

[0114] R 4 is preferably a hydrogen atom, an alkyl group, an aryl group, a heteroaryl group, or a group represented by -BR 4x R 4y more preferably a hydrogen atom, an alkyl group, an aryl group, or a group represented by -BR 4x R 4y and particularly preferably a group represented by -BR 4x R 4y The substituent represented by R 4x R 4y is preferably a halogen atom, an alkyl group, an alkoxy group, an aryl group, or a heteroaryl group, more preferably an alkyl group, an aryl group, or a heteroaryl group, and particularly preferably an aryl group. These groups may further have substituents. The two R 4 in the general formula (12) may be the same or different.

[0115] The following are specific examples of pyrrolopyrrole compounds. In the following structural formulas, Ph represents a phenyl group. However, the present invention is not limited to these examples.

[0116] [ka]

[0117] [Indigo compounds] The indigo compound is not particularly limited, and any known compound can be used. For example, compounds represented by the following general formula (13) or general formula (14) can be used.

[0118] General formula (13) General formula (14) [ka]

[0119] In general formulas (13) and (14), X1 to X 40 Each of these independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted arylalkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an amino group, an optionally substituted alkylamino group, an optionally substituted arylamino group, a cyano group, a halogen atom, a nitro group, a hydroxyl group, -SO3H; -COOH; and monovalent to trivalent metal salts of these acidic groups; or alkylammonium salts. M represents a metal atom.

[0120] Examples of alkyl groups that may have substituents include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl, n-octyl, stearyl, and 2-ethylhexyl groups. Examples of alkyl groups with substituents include trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, and 2,4-dichlorobenzyl groups.

[0121] Examples of the "aryl group" which may have substituents include a phenyl group, a naphthyl group, anthuryl group, and the like. Examples of "substituted aryl groups" include p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p-methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4,5,8-trichloro-2-naphthyl group, anthraquinonyl group, and 2-aminoanthraquinonyl group.

[0122] Examples of alkoxyl groups that may have substituents include linear or branched alkoxyl groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, neopentyloxy, 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy. Examples of "substituted alkoxyl groups" include trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2-ditrifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, and benzyloxy groups.

[0123] Examples of "aryloxy groups" that may have substituents include phenoxy, naphthoxy, and anthuryloxy groups, while examples of "substituted aryloxy groups" include p-methylphenoxy, p-nitrophenoxy, p-methoxyphenoxy, 2,4-dichlorophenoxy, pentafluorophenoxy, and 2-methyl-4-chlorophenoxy groups.

[0124] Examples of "arylalkyl groups that may have substituents" include benzyl group, 2-phenylpropanyl group, styryl group, diphenylmethyl group, triphenylmethyl group, and the like.

[0125] Examples of "cyclic alkyl groups" that may have substituents include cyclopentyl groups, cyclohexyl groups, and adamantyl groups. Examples of "substituted cycloalkyl groups" include 2,5-dimethylcyclopentyl groups and 4-tert-butylcyclohexyl groups.

[0126] Examples of alkylthio groups that may have substituents include methylthio, ethylthio, propylthio, butylthio, pentylthio, hexylthio, octylthio, decylthio, dodecylthio, and octadecylthio groups. Examples of "alkylthio groups having substituents" include methoxyethylthio groups, aminoethylthio groups, benzylaminoethylthio groups, methylcarbonylaminoethylthio groups, and phenylcarbonylaminoethylthio groups.

[0127] The "arylthio group" of the arylthio group which may have a substituent includes, for example, phenylthio group, 1-naphthylthio group, 2-naphthylthio group, 9-anthrylthio group and the like. Examples of the "arylthio group having a substituent" include chlorophenylthio group, trifluoromethylphenylthio group, cyanophenylthio group, nitrophenylthio group, 2-aminophenylthio group, 2-hydroxyphenylthio group and the like.

[0128] The "alkylamino group" of the alkylamino group which may have a substituent includes, for example, methylamino group, ethylamino group, propylamino group, butylamino group, pentylamino group, hexylamino group, heptylamino group, octylamino group, nonylamino group, decylamino group, dodecylamino group, octadecylamino group, isopropylamino group, isobutylamino group, isopentylamino group, sec-butylamino group, tert-butylamino group, sec-pentylamino group, tert-pentylamino group, tert-octylamino group, neopentylamino group, cyclopropylamino group, cyclobutylamino group, cyclopentylamino group, cyclohexylamino group, cycloheptylamino group, cyclooctylamino group, cyclododecylamino group, 1-adamantamino group, 2-adamantamino group and the like.

[0129] The "arylamino group" of the arylamino group which may have a substituent includes, for example, anilino group, 1-naphthylamino group, 2-naphthylamino group, o-toluidino group, m-toluidino group, p-toluidino group, 2-biphenylamino group, 3-biphenylamino group, 4-biphenylamino group, 1-fluorenamino group, 2-fluorenamino group, 2-thiazolamino group, p-terphenylamino group and the like.

[0130] Examples of the halogen atom include fluorine, chlorine, bromine and iodine.

[0131] Examples of acidic groups include -SO3H and -COOH. Examples of monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, and aluminum salts. Examples of alkylammonium salts of acidic groups include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, and stearylamine, and quaternary alkylammonium salts such as palmityltrimethylammonium, lauryltrimethylammonium, dilauryldimethylammonium, and distearyldimethylammonium salts.

[0132] Of the substituents listed above, X1 to X 40 Preferred substituents include hydrogen atoms, methyl groups, methoxy groups, fluorine atoms, chlorine atoms, bromine atoms, and -SO3H.

[0133] M represents a metal atom. Examples of metal atoms include Zn, Co, Ni, Ru, Pt, Mn, Sn, Ti, and Ba. Among these, divalent metal atoms are preferred, and Zn, Co, and Ni are more preferred.

[0134] The following are specific examples of indigo compounds. However, the present invention is not limited to these examples.

[0135] [ka] [ka] [ka] [ka]

[0136] [Phthalocyanine compounds] The phthalocyanine compound is not particularly limited, and any known compound can be used, except for compound (A1) represented by general formula (1). For example, a compound represented by the following general formula (15) can be used.

[0137] General formula (15) [ka]

[0138] In general formula (15), multiple R 1 Each of these independently represents an alkyl group which may have substituents, or an aryl group which may have substituents. 2 Each of the following independently represents a hydrogen atom, a halogen atom, or an alkyl group which may have substituents. M represents a derivative of two hydrogen atoms, a divalent metal atom, or a trivalent or tetravalent metal atom. Each of the n independently represents an integer from 3 to 6.

[0139] R 1 The alkyl group, which may have substituents represented by , preferably has 1 to 20 carbon atoms, more preferably 1 to 12, and particularly preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, with linear or branched being preferred. Specifically, examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group, stearyl group, 2-ethylhexyl group, 3-methyl-1-isopropylbutyl group, 3,5,5-trimethylhexyl group, cyclohexyl group, cyclopentyl group, cyclohexylmethyl group, cyclohexylethyl group, cyclopentylmethyl group, and cyclopentylethyl group.

[0140] R 1 Examples of substituents on an alkyl group that may have substituents represented by include alkoxy groups, alkylthio groups, carboxyl groups, thiol groups, halogen groups, amino groups, cyano groups, nitro groups, and the like.

[0141] R 1The aryl group, which may have substituents represented by , preferably has 6 to 30 carbon atoms, and more preferably 6 to 20. Specifically, examples include phenyl group, phenethyl group, o-, m- or p-tolyl group, 2,3- or 2,4-xylyl group, mesityl group, naphthyl group, anthryl group, phenanthryl group, biphenylyl group, etc.

[0142] R 1 Examples of substituents on an aryl group that may have substituents represented by include alkoxy groups, alkylthio groups, carboxyl groups, thiol groups, halogen groups, amino groups, cyano groups, nitro groups, and the like.

[0143] Multiple R 1 They may be the same or different, but it is preferable that they be the same.

[0144] R 2 The alkyl group which may have substituents represented by R 1 Examples include alkyl groups that may have substituents represented by .

[0145] Multiple R 2 They may be the same or different, but it is preferable that they be the same.

[0146] R 2 A hydrogen atom is preferred.

[0147] When M represents two hydrogen atoms, the NMN portion of general formula (15) forms a structure represented as two NH groups. Examples of divalent metal atoms represented by M include iron, magnesium, nickel, cobalt, copper, palladium, zinc, vanadium, titanium, indium, manganese, and tin. Examples of derivatives of the trivalent or tetravalent metal atom represented by M include AlCl, AlBr, AlOH, InCl, InBr, InI, SiCl2, SiBr2, Si(OH)2, GeCl2, GeBr2, GeI2, SnCl2, SnBr2, SnI2, Sn(OH)2, VO, TiO2, etc. Among these, copper, zinc, cobalt, nickel, iron, tin, indium, SnCl2, AlCl, VO, and TiO2 are preferred as M, with VO being more preferred.

[0148] [Croconium compounds] The croconium compound is not particularly limited, and known compounds can be used. For example, a compound represented by the following general formula (16) can be used.

[0149] General formula (16) [ka]

[0150] In general formula (16), X1 and X2 each independently represent an aryl group, a heterocyclic group, or a group represented by the following general formula (17).

[0151] General formula (17) [ka]

[0152] In general formula (17), X3 represents a heterocyclic group, Y1 to Y3 each independently represent a hydrogen atom or an alkyl group, and n1 represents an integer of 0 or more. Y1 and Y2, Y1 and X3, and Y2 and Y3 may each be bonded to each other to form a ring, and if n1 is 2 or more, multiple Y2 and Y3 may be the same or different. * represents a bond.

[0153] The number of carbon atoms in the aryl groups represented by X1 and X2 is preferably 6 to 48, more preferably 6 to 22, and particularly preferably 6 to 12.

[0154] The heterocyclic groups represented by X1 to X3 are preferably 5-membered or 6-membered heterocyclic groups. Furthermore, the heterocyclic groups are preferably monocyclic heterocyclic groups or fused heterocyclic groups with 2 to 8 fusion numbers, more preferably monocyclic heterocyclic groups or fused heterocyclic groups with 2 to 4 fusion numbers, and particularly preferably monocyclic heterocyclic groups or fused heterocyclic groups with 2 fusion numbers. The heteroatoms constituting the ring of the heterocyclic group include nitrogen atoms, oxygen atoms, and sulfur atoms, with nitrogen atoms and sulfur atoms being preferred. The number of heteroatoms constituting the ring of the heterocyclic group is preferably 1 to 3, and more preferably 1 or 2.

[0155] The number of carbon atoms in the alkyl group represented by Y1 to Y3 is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 8. The alkyl group may be linear, branched, or cyclic.

[0156] n1 is preferably an integer between 0 and 2, and more preferably 0 or 1.

[0157] When Y1 and Y2, Y1 and X3, and Y2 and Y3 each form a ring with each other, the preferred linking group is a divalent linking group selected from the group consisting of -CO-, -O-, -NH-, alkylene groups having 1 to 10 carbon atoms, and combinations thereof. The alkylene group may be unsubstituted or may have substituents. Examples of substituents include substituent T, which will be described later.

[0158] The groups represented by X1 and X2 preferably have substituents. Examples of substituents include substituent T, which will be described later.

[0159] {substituent T} The substituent T can be a halogen atom, cyano group, nitro group, alkyl group, alkenyl group, alkynyl group, aryl group, heteroaryl group, or -OR 1 , -COR 1 ,-COOR 1 , -OCOR 1 , -NR 1 R 2 , -NHCOR 1 ,-CONR 1 R 2 ,-NHCONR 1R 2 , -NHCOOR 1 , -SR 1 , -SO2R 1 , -SO2R 1 , -NHSO2R 1 or -SO2NR 1 R 2 Examples include R. 1 and R 2 Each of these independently represents a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a heteroaryl group. 1 and R 2 They may combine to form a ring. Note that -COOR 1 and -SO2OR 1 R 1 In the case of hydrogen, the hydrogen atom may dissociate, or it may exist in a salt state.

[0160] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 15, and particularly preferably 1 to 8. The alkyl group may be linear, branched, or cyclic, with linear or branched being preferred. The number of carbon atoms in the alkenyl group is preferably 2 to 20, more preferably 2 to 12, and particularly preferably 2 to 8. The alkenyl group may be linear, branched, or cyclic, with linear or branched being preferred. The number of carbon atoms in the alkynyl group is preferably 2 to 40, more preferably 2 to 30, and particularly preferably 2 to 25. The alkynyl group may be linear, branched, or cyclic, with linear or branched being preferred. The number of carbon atoms in the aryl group is preferably 6 to 30, more preferably 6 to 20, and particularly preferably 6 to 12. The heteroaryl group is preferably a monocyclic heteroaryl group or a fused ring heteroaryl group with 2 to 8 condensation rings, and more preferably a monocyclic heteroaryl group or a fused ring heteroaryl group with 2 to 4 condensation rings. The heteroatoms constituting the ring of the heteroaryl group are preferably nitrogen atoms, oxygen atoms, or sulfur atoms. The heteroaryl group is preferably a 5-membered ring or a 6-membered ring. The number of carbon atoms constituting the ring of the heteroaryl group is preferably 3 to 30, more preferably 3 to 18, and particularly preferably 3 to 12. The alkyl group, alkenyl group, alkynyl group, aryl group, and heteroaryl group may have substituents or be unsubstituted. Examples of substituents include the substituent T mentioned above.

[0161] Furthermore, in general formula (16), the cation exists in a delocalized state as follows.

[0162] [ka]

[0163] The following are specific examples of crokonium compounds. However, the present invention is not limited to these.

[0164] [ka]

[0165] Compound (A2) can be used alone or in combination of two or more compounds.

[0166] From the viewpoint of infrared blocking properties and foreign matter suppression, the content of the near-infrared absorbing compound (A) is preferably 0.5 to 70% by mass, more preferably 1 to 50% by mass, and particularly preferably 2 to 35% by mass, based on 100% by mass of the non-volatile content of the composition.

[0167] [Resin (B)] The composition of the present invention comprises resin (B).

[0168] Resin (B) is used, for example, to disperse particles such as near-infrared absorbing compounds (A) in a composition, or to impart resistance to the film. Resin (B) used primarily to disperse particles such as near-infrared absorbing compounds (A) is also called a dispersion resin, and resin (B) used to impart resistance to the film is also called a binder resin. However, these uses of resin (B) are just examples, and it can be used for other purposes as well.

[0169] Resin (B) is not particularly limited, and any known resin can be used. Examples include (meth)acrylic resin, styrene resin, styrene / (meth)acrylic resin, epoxy resin, urethane resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamide-imide resin, and cyclic olefin resin. These can be used alone or in combination of two or more types.

[0170] The weight-average molecular weight (Mw) of resin (B) is preferably 3,000 to 200,000, and more preferably 4,000 to 150,000.

[0171] The content of resin (B) is preferably 1 to 95% by mass, and more preferably 5 to 80% by mass, based on 100% by mass of the nonvolatile content of the composition.

[0172] (Resin (B1)) From the viewpoint of infrared shielding and suppression of foreign matter, resin (B) preferably contains a resin (B1) having a basic group (hereinafter also simply referred to as resin (B1)). The resin (B1) having a basic group is not particularly limited, and known resins can be used. For example, a copolymer of a monomer having a basic group and another copolymerizable monomer can be used. Furthermore, the resin (B1) having basic groups may also have acidic groups. In this case, a resin in which the content of basic groups is greater than the content of acidic groups is preferred.

[0173] Basic groups include, for example, primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocycles and other groups containing nitrogen atoms.

[0174] The resin (B1) having a basic group preferably has at least one monomer unit selected from the group consisting of monomer units represented by the following general formulas (18) to (20) as the basic group.

[0175] General formula (18) [ka]

[0176] In general formula (18), R1 to R3 each independently represent a hydrogen atom or a linear or cyclic hydrocarbon group which may have substituents, and two or more of R1 to R3 may be bonded to each other to form a cyclic structure. R4 represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y - This represents the paired anion.

[0177] General formula (19) [ka]

[0178] In general formula (19), R5 and R6 each independently represent a hydrogen atom or a cyclic or cyclic hydrocarbon group which may have substituents, and R5 and R6 may bond to each other to form a cyclic structure. R4 represents a hydrogen atom or a methyl group, and X represents a divalent linking group.

[0179] General formula (20) [ka]

[0180] In general formula (20), R7 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxyradical group, or OR 12 Represents R 12R8, R9, R 10 , R 11 Each of these independently represents a methyl group, an ethyl group, or a phenyl group. R4 represents a hydrogen atom or a methyl group, and X represents a divalent linking group.

[0181] In general formula (18), R1 to R3 are more preferably alkyl groups having 1 to 4 carbon atoms, which may have substituents, or aralkyl groups having 7 to 16 carbon atoms, which may have substituents, and particularly preferably methyl, ethyl, propyl, butyl, and benzyl groups.

[0182] In general formula (19), R5 and R6 are more preferably alkyl groups having 1 to 4 carbon atoms, which may have substituents, and methyl, ethyl, propyl, and butyl groups are particularly preferred.

[0183] In R7 of general formula (20), examples of alkyl groups having 1 to 18 carbon atoms include linear, branched, and cyclic alkyl groups, specifically including methyl, ethyl, n-propyl, isopropyl, n-butyl, t-butyl, n-hexyl, cyclohexyl, n-octyl, and hexadecyl groups. Examples of aryl groups having 6 to 20 carbon atoms include the phenyl group, 1-naphthyl group, and 2-naphthyl group. Aralkyl groups having 7 to 12 carbon atoms include, for example, groups in which an alkyl group having 1 to 8 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms. Specifically, examples include the benzyl group, phenethyl group, α-methylbenzyl group, and 2-phenylpropan-2-yl group. Furthermore, examples of acyl groups include alkanoyl groups and alloyl groups having 2 to 8 carbon atoms, specifically acetyl groups, benzoyl groups, and the like. Among these, hydrogen atoms, alkyl groups having 1 to 5 carbon atoms, and oxy radical groups are preferred, hydrogen atoms and methyl groups are more preferred, and methyl groups are particularly preferred.

[0184] In general formulas (18) to (20), the divalent linking group X is, for example, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, or a -CONH-R 13 -,-COO-R 14 -(However, R 13 and R 14 Examples include single bonds, methylene groups, alkylene groups having 2 to 10 carbon atoms, or ether groups (alkyloxyalkyl groups) having 2 to 10 carbon atoms, preferably -COO-R 1 4 -. Also, in general formula (16), the Y of the pair anion - For example, Cl - , Br - , I - ClO4 - BF4, CH3COO - PF6 - These are some examples.

[0185] Monomers that form monomer units represented by general formula (18) include, for example, alkyl (meth)acrylate quaternary ammonium salts such as (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, (meth)acryloyloxyethyldimethylbenzylammonium chloride, and (meth)acryloyloxyethylmethylmorpholinoammonium chloride; alkyl (meth)acryloylamide quaternary ammonium salts such as (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloylaminoethyltriethylammonium chloride, and (meth)acryloylaminoethyldimethylbenzylammonium chloride; dimethyldiallylammonium methyl sulfate; and trimethylvinylphenylammonium chloride.

[0186] Monomers that form monomer units represented by general formula (19) include, for example, (meth)acrylates having a tertiary amino group such as N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate; and (meth)acrylamides having a tertiary amino group such as N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl (meth)acrylamide.

[0187] Examples of monomers that form monomer units represented by general formula (20) include the following compounds. In the following structural formulas, R4 represents hydrogen or a methyl group.

[0188] [ka]

[0189] Among the above compounds, 2,2,6,6-tetramethylpiperidyl methacrylate and 1,2,2,6,6-pentamethylpiperidyl methacrylate are preferred, and 1,2,2,6,6-pentamethylpiperidyl methacrylate is more preferred.

[0190] The monomer units represented by general formulas (18) to (20) may be present individually or in combination of two or more types.

[0191] The content of monomer units represented by general formulas (18) to (20) is preferably 5 to 90 mol%, and more preferably 10 to 80 mol%, of the total constituent units of resin (B1).

[0192] Resin (B1) may have monomer units other than monomer units having a basic group (also called other monomer units). Monomers that form other monomer units include, for example, linear or branched alkyl(meth)acrylates such as methyl(meth)acrylate, ethyl(meth)acrylate, propyl(meth)acrylate, isopropyl(meth)acrylate, butyl(meth)acrylate, isobutyl(meth), tertiarybutyl(meth)acrylate, isoamyl(meth)acrylate, octyl(meth)acrylate, isooctyl(meth)acrylate, 2-ethylhexyl(meth)acrylate, cetyl(meth)acrylate, decyl(meth)acrylate, isodecyl(meth)acrylate, lauryl(meth)acrylate, tridecyl(meth)acrylate, isomiristyl(meth)acrylate, stearyl(meth)acrylate, and isostearyl(meth)acrylate; Cyclohexyl (meth)acrylates such as tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate; Heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate and 3-methyl-3-oxetanyl (meth)acrylate; (Meth)acrylates having aromatic rings such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate (Poly)alkylene glycol monoalkyl ether (meth)acrylates such as methyl ether (meth)acrylate, tripropylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, polypropylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monolauryl ether (meth)acrylate, polyethylene glycol monostearyl ether (meth)acrylate, and octoxy polyethylene glycol-polypropylene glycol (meth)acrylate; (Poly)alkylene glycol (meth)acrylates having aromatic rings, such as phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethyl (meth)acrylate, paracumylphenoxyethylene glycol (meth)acrylate, paracumylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, and nonylphenoxypoly(ethylene glycol-propylene glycol) (meth)acrylate; (Meth)acrylates having alkyloxysilyl groups, such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate; (meth)acryloxy-modified polydimethylsiloxanes (silicone macromers); Examples include N-substituted (meth)acrylamides such as (meth)acrylamide, dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; and nitriles such as (meth)acrylonitrile. Also, styrene and styrene compounds such as α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and vinyl fatty acid compounds such as vinyl acetate and vinyl propionate; Examples include unsaturated carboxylic acids such as (meth)acrylic acid, (meth)acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, and crotonic acid. These monomers can be used individually or in combination of two or more.

[0193] Furthermore, resin (B1) can also suitably be a resin in which a compound represented by the following general formula (21) or general formula (22) is bonded to a part of the basic group to form a salt.

[0194] General formula (21) [ka]

[0195] In general formula (21), R1 and R 2 Each of these independently consists of a hydrogen atom, a hydroxyl group, a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have substituents, or -OR 4 Represents R 4 R represents a (meth)acryloyl group via a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl or benzyl group, or an alkylene group having 1 to 4 carbon atoms. However, R 1 and R 2 At least one of them is a group containing a carbon atom.

[0196] General formula (22) [ka]

[0197] In general formula (22), R 3 This includes linear, branched, or cyclic alkyl groups having 1 to 20 carbon atoms, vinyl groups, optionally substituted phenyl or benzyl groups, or -OR 4 Represents R 4 This represents a (meth)acryloyl group via a linear, branched, or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, an optionally substituted phenyl or benzyl group, or an alkylene group having 1 to 4 carbon atoms.

[0198] Compounds represented by general formula (21) include, for example, monobutyl phosphate, dibutyl phosphate, methyl phosphate, dibenzyl phosphate, diphenyl phosphate, phenylphosphinic acid, phenylphosphonic acid, and dimethacryloyloxyethyl acid phosphate.

[0199] Compounds represented by general formula (22) include, for example, benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethylsulfuric acid, monoethylsulfuric acid, and mono-n-propylsulfuric acid. Hydrates such as p-toluenesulfonic acid monohydrate may also be used.

[0200] Examples of resin (B1) structures include random structures, block structures, graft structures, comb-shaped structures, and star-shaped structures. Among these, the block structure is preferred from the viewpoint of suppressing foreign matter.

[0201] From the viewpoint of suppressing foreign matter, the amine value of resin (B1) is preferably 20 to 250 mg KOH / g, and more preferably 30 to 200 mg KOH / g.

[0202] Resin (B1) can be used alone or in combination of two or more types.

[0203] From the viewpoint of suppressing foreign matter, the content of resin (B1) is preferably 3 to 200 parts by mass, and more preferably 5 to 150 parts by mass, per 100 parts by mass of near-infrared absorbing compound (A).

[0204] (Resin (B2)) From the viewpoint of the film's resistance to organic solvents, alkaline developers, etc., resin (B) preferably contains resin (B2) (hereinafter also simply referred to as resin (B2)) which has at least one selected from the group consisting of alicyclic hydrocarbon-containing monomer units, aromatic ring-containing monomer units, and heterocyclic-containing monomer units. More preferably, it contains one selected from the group consisting of alicyclic hydrocarbon-containing monomer units and aromatic ring-containing monomer units. Examples of resins (B2) include copolymers of at least one alicyclic hydrocarbon-containing monomer, an aromatic ring-containing monomer, and a heterocyclic-containing monomer with other monomers copolymerizable therewith.

[0205] Examples of alicyclic hydrocarbon-containing monomers include isobolonyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, adamantyl (meth)acrylate, 2-methyl-2-adamantyl (meth)acrylate, and 2-ethyl-2-adamantyl (meth)acrylate. Among these, from the viewpoint of film resistance, alicyclic hydrocarbon-containing monomers with a homopolymer glass transition temperature of 80°C or higher are preferred, with isobolonyl methacrylate, adamantyl methacrylate, and dicyclopentanyl methacrylate being more preferred.

[0206] The content of alicyclic hydrocarbon-containing monomer units is preferably 1 to 50 mol%, and more preferably 5 to 40 mol%, of the total constituent units of the resin (B2).

[0207] Examples of aromatic ring-containing monomers include benzyl (meth)acrylate, phenyl (meth)acrylate, phenoxyethyl (meth)acrylate, ethylene oxide (EO) or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, N-phenylmaleimide, styrene, α-methylstyrene, and vinylnaphthalene. Among these, aromatic ring-containing monomers with a homopolymer glass transition temperature of 80°C or higher are preferred from the viewpoint of film resistance, and styrene and α-methylstyrene are more preferred.

[0208] The content of aromatic ring-containing monomer units is preferably 1 to 50 mol%, and more preferably 5 to 40 mol%, of the total constituent units of the resin (B2).

[0209] Examples of heterocyclic monomers include tetrahydrofurfuryl(meth)acrylate, (2-methyl-2-ethyl-1,3-dioxolan-4-yl)methyl(meth)acrylate, 4-acryloylmorpholine, N-vinyl-2-pyrrolidone, glycidyl(meth)acrylate, and methylglycidyl(meth)acrylate. Among these, glycidyl(meth)acrylate is preferred from the viewpoint of film resistance.

[0210] The content of heterocyclic monomer units is preferably 1 to 50 mol%, and more preferably 5 to 40 mol%, of the total constituent units of the resin (B2).

[0211] The resin (B2) may contain monomer units other than alicyclic hydrocarbon-containing monomer units, aromatic ring-containing monomer units, and heterocyclic-containing monomer units (hereinafter also referred to as other monomer units). Other monomers that form monomer units include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate; Hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, and glycerol mono(meth)acrylate; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; Examples include unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid. These monomers can be used individually or in combination of two or more.

[0212] Furthermore, from the viewpoint of film resistance, it is preferable that the resin (B2) has polymerizable unsaturated monomer units. Methods for introducing polymerizable unsaturated monomer units include reacting epoxy groups in the resin with an unsaturated carboxylic acid such as (meth)acrylic acid, or reacting hydroxyl groups in the resin with a compound having an isocyanate group and a polymerizable unsaturated group.

[0213] Resin (B2) can be used alone or in combination of two or more types.

[0214] [Curable compound (C)] The composition of the present invention may contain a curable compound (C).

[0215] The curable compound (C) is not particularly limited as long as it is a compound that can be cured by radicals, acids, or heat; any known compound can be used. Examples include compounds having polymerizable unsaturated groups, compounds having epoxy groups, compounds having oxetanyl groups, compounds having methylol groups, compounds having alkoxysilyl groups, and so on.

[0216] (Compounds having polymerizable unsaturated groups) Compounds having polymerizable unsaturated groups may be in the form of monomers or oligomers. Examples of polymerizable unsaturated groups include vinyl groups, styryl groups, (meth)allyl groups, (meth)acryloyl groups, and (meth)acryloyloxy groups.

[0217] Compounds having polymerizable unsaturated groups include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, tricyclodecanyl (meth)acrylate, 2-acryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethyl acid phosphate, phenoxytetraethylene glycol (meth)acrylate, and phenoxyhexyl Ethylene glycol (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, dimethylol tricyclodecane dimethanol di(meth)acrylate, isocyanurate EO modified di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, ethylene glycol diglycidyl ether di(meth)acrylate, propylene glycol diglycidyl ether di(meth)acrylate Examples include rilate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile, etc.

[0218] Examples of commercially available compounds having polymerizable unsaturated groups include, for example, KAYARAD DPCA-20, DPCA-30, DPCA-60, R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330 from Nippon Kayaku Co., Ltd., and Viscoat #2500P, #310HP, #335HP, #700, #295, #330, #360, # from Osaka Organic Chemical Industry Co., Ltd. GPT, #400, #405, Viscoat #1000LT, and Aronix M-5300, M-5400, M-5700, M-510, M-520, M-521, M-303, M-305, M-306, M-309, M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408 (manufactured by Toagosei Co., Ltd.) , M-211B, M-920, M-930, M-933, M-940, M-101A, MT-3041, MT-3042, OT-1523, OT-1524, β-CEA from Daicel Ornex, AH-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 from Kyoeisha Chemical, NK Ester 701A, ABE-300, A-DOG, A-DCP, A-BP from Shin Nakamura Chemical E-4, A-TMPT-9EO, AT-20E, A-GLY-3E, A-9200YN, A-9300, ATM-35E, AD-TMP, UA-4200, UA-122P, UA-7100, UA-1100H, U-6LPA, UA-33H, U-10HA, U-15HA, EBECRYL40, 130, 140, 145, 1290, 896, OTA480, KRM8452 from Daicel Ornex, OGSOL EA-0200, EA-0300, GA-5060P, GA-2800 from Osaka Gas Chemical Co., Ltd., Miwon Specialty Chemical Co.Examples include Miramer HR6060, HR6100, HR6200, SP-1106, SP-1108 from , Ltd., CN2301, CN2302, CN2303 from SARTOMER, and Etercure6361-100, Etercure6362-100, Etercure6363 from Eternal Materials.

[0219] (Compounds containing epoxy groups) Compounds containing epoxy groups can be low molecular weight compounds or high molecular weight compounds such as resins. Examples include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnolbornene, tetrahydroxy Examples include polymers of droindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.; polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.); polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.); polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.); polycondensates of bisphenols and various aldehydes; glycidyl ether epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins obtained by glycidylating alcohols, etc.

[0220] Compounds containing epoxy groups are preferably those having 2 to 50 epoxy groups in the molecule, and more preferably those having 10 to 30 epoxy groups. Furthermore, the epoxy equivalent of the epoxy-containing compound is preferably 50 to 400 g / eq, and more preferably 100 to 200 g / eq. Note that epoxy equivalent is defined as the mass of the epoxy-containing compound containing 1 equivalent of epoxy groups.

[0221] Commercially available epoxy group compounds include, for example, Epicote 807, 815, 825, 827, 828, 190P, 191P from Shell Epoxy Co., Ltd., TECHMORE VG3101L from Mitsui Chemicals, Inc., EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 from Nippon Kayaku Co., Ltd., Epicote 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 from Japan Epoxy Resin Co., Ltd., Celoxide 2021, EHPE-3150, Epolid GT401 from Daicel Chemical Industries, Ltd., and Denacol EX-211, 212, 252, 313, 3 from Nagase ChemteX Corporation. Examples include 14, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721, TEPIC-L, H, S from Nissan Chemical Industries, and EPICLON830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, HP-9500 from DIC Corporation.

[0222] (Compounds containing an oxetanyl group) Compounds containing an oxetanyl group may have one oxetanyl group in their molecule, but compounds having two or more oxetanyl groups are preferred. Furthermore, the oxetane equivalent of the compound containing an oxetanyl group is preferably 150 to 600 g / eq, and more preferably 180 to 500 g / eq. Note that the oxetane equivalent is defined as the mass of the compound containing an oxetanyl group containing one equivalent of an oxetanyl group.

[0223] Compounds having an oxetanyl group include, for example, (3-ethyloxetan-3-yl)methyl(meth)acrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), and 1,4-bis[(3-ethyl-3-hydroxymethyl]biphenyl). [(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethyl] [(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethyl) Examples include xy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, and EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether.

[0224] Examples of commercially available compounds containing an oxetanyl group include OXE-10 and 30 from Osaka Organic Chemical Industry Co., Ltd., Aronoxetane OXT-101, 212, 121, and 221 from Toagosei Co., Ltd., and ETERNACOLL EHO, HBOX, OXMA, OXBP, and OXIPA from Ube Industries, Ltd.

[0225] (Compounds containing a methylol group) Compounds containing a methylol group include, for example, compounds in which the methylol group is bonded to a nitrogen atom or a carbon atom that forms an aromatic ring.

[0226] Examples of compounds having a methylol group include alkoxymethylated melamine, methylolated melamine, alkoxymethylated benzoguanamine, methylolated benzoguanamine, alkoxymethylated glycoluryl, methylolated glycoluryl, and alkoxymethylated urea.

[0227] Examples of commercially available compounds containing a methylol group include Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 from Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 from Nippon Cytec Industries Co., Ltd.

[0228] (Compounds containing an alkoxysilyl group) Compounds having an alkoxysilyl group are preferably those in which the alkoxysilyl group is a dialkoxysilyl group or a trialkoxysilyl group. Furthermore, compounds in which the alkoxy group has 1 to 5 carbon atoms are preferred, and compounds with 1 to 3 carbon atoms are more preferred.

[0229] Compounds containing an alkoxysilyl group include, for example, methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, and trifluoropropyl Trimethoxysilane, hexamethyldisilazane, vinyltrimethoxysilane, vinyltriethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, p-styryltrimethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxy Propyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propyl Examples include amines, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, tris-(trimethoxysilylpropyl)isocyanurate, 3-ureidopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, and 3-isocyanatetopropyltriethoxysilane.

[0230] Examples of commercially available compounds containing alkoxysilyl groups include KBM-13, KBM-22, KBM-103, KBE-13, KBE-22, KBE-103, KBM-3033, KBE-3033, KBM-3063, KBM-3066, KBM-3086, KBE-3063, KBE-3083, KBM-3103, KBM-3066, and KBM-7103, all manufactured by Shin-Etsu Silicone Co., Ltd. SZ-31, KPN-3504, KBM-1003, KBE-1003, KBM-303, KBM-402, KBM-403, KBE-402, KBE-403, KBM-1403, KBM -502, KBM-503, KBE-502, KBE-503, KBM-5103, KBM-602, KBM-603, KBM-903, KBE-903, KBE-9103, KBM-57 3, KBM-575, KBM-9659, KBE-585, KBM-802, KBM-803, KBE-846, KBE-9007, X-12-1048, X-12-1050, X-12- 9815, X-12-9845, X-12-1154, X-12-972F, X-12-1159L, X-40-1053, X-41-1059A, X-41-1056, X-41-180 Examples include 5, X-41-1818, X-41-1810, X-40-2651, X-40-2655A, KR-513, KC-89S, KR-500, X-40-9225, X-40-9246, X-40-9250, KR-401N, X-40-9227, X-40-9247, KR-510, KR-9218, KR-213, X-40-2308, X-40-9238, etc.

[0231] The curable compound (C) can be used alone or in combination of two or more types.

[0232] The content of the curable compound (C) is preferably 0.1 to 60% by mass of 100% by mass of the nonvolatile content of the composition.

[0233] [Polymerization initiator (D)] The composition of the present invention may contain a polymerization initiator (D). In particular, if the composition of the present invention contains a compound having a polymerizable unsaturated group, it is preferable to include a polymerization initiator (D) from the viewpoint of film resistance.

[0234] The polymerization initiator (D) is not particularly limited, and known compounds can be used. For example, compounds that generate radicals by the action of light or heat to initiate or accelerate the radical polymerization reaction can be used. A polymerization initiator that generates radicals in response to light (hereinafter also simply referred to as a photopolymerization initiator) is preferably a compound that generates radicals in response to light from ultraviolet to visible light. A polymerization initiator that generates radicals by heat (hereinafter also simply referred to as a thermal polymerization initiator) may be a compound that generates radicals by the action of heat and light.

[0235] Examples of photopolymerization initiators include acetophenone compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; Triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyl oxime)], or etanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole3-yl]-,1-(O-acetyl oxime); Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; and carbazole compounds.

[0236] Commercially available products include: acetophenone compounds such as Omnirad907, 369E, 379EG, 127, 184, 1173, and 2959 from IGM Resins; acylphosphine compounds such as Omnirad819 and TPO from IGM Resins; oxime compounds such as IRGACURE OXE-01, 02, 03, and 04 from BASF Japan; N-1919, NCI-730, 831, and 930 from ADEKA; and TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 from Changzhou Strong New Materials Co., Ltd. Examples include Omnirad 1312, 1314, and 1316 from Resins, SPI-02, 03, 04, 05, 06, and 07 from Samyang Corporation, and DFI-020, 306, and EOX-01 from Daito Chemix. Other examples include compounds described in Japanese Patent Publication No. 2007-210991, Japanese Patent Publication No. 2009-179619, Japanese Patent Publication No. 2010-037223, Japanese Patent Publication No. 2010-215575, Japanese Patent Publication No. 2011-020998, International Publication No. 2015 / 036910, Japanese Patent Publication No. 2019-507108, Japanese Patent Publication No. 2019-528331, and International Publication No. 2021 / 175855.

[0237] The photopolymerization initiator is preferably at least one compound selected from the compounds represented by the following general formula (23) and the compounds represented by the following general formula (24).

[0238] [ka]

[0239] In general formula (23), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R3 represents a hydrogen atom or a monovalent substituent. In general formula (24), X1 and X2 each independently represent a carbonyl bond (-CO-) or a single bond. R4 represents an alkyl group having 1 to 20 carbon atoms, and R5 and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. R7 and R8 each independently represent an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms.

[0240] In general formula (23), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. Alkyl groups having 1 to 8 carbon atoms may be linear, branched, cyclic, or combined. Examples include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, t-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, and cyclohexylmethyl groups. Among these, linear alkyl groups having 3 to 8 carbon atoms are preferred, and linear alkyl groups having 4 to 6 carbon atoms are more preferred.

[0241] In general formula (23), R3 represents a hydrogen atom or any monovalent substituent. Examples of monovalent substituents include C1-C20 alkyl groups such as methyl and ethyl groups; C1-C20 alkoxy groups such as methoxy and ethoxy groups; halogen atoms such as F, Cl, Br, and I; C1-C20 acyl groups; C1-C20 alkyl ester groups; C1-C20 alkoxycarbonyl groups; C1-C20 halogenated alkyl groups, C4-C20 aromatic ring groups; amino groups; C1-C20 aminoalkyl groups; hydroxyl groups; nitro groups; cyano groups; benzoyl groups which may have substituents; and tenoyl groups which may have substituents. Examples of substituents that the benzoyl or tenoyl group may have include C1-C10 alkyl groups, C1-C10 alkoxy groups, and C1-C10 alkoxycarbonyl groups. Among these, from the viewpoint of radical generation efficiency, hydrogen atoms and nitro groups are preferred, and hydrogen atoms are more preferred.

[0242] Examples of methods for producing compounds represented by general formula (23) include those described in Japanese Patent Publication No. 2019-507108 and Japanese Patent Publication No. 2019-528331.

[0243] The following are specific examples of compounds represented by general formula (23). However, the present invention is not limited to these examples.

[0244] [ka]

[0245] In general formula (24), X1 and X2 each independently represent a carbonyl bond (-CO-) or a single bond. Of these, from the viewpoint of solubility in organic solvents, it is preferable that at least one of X1 and X2 is a carbonyl bond (-CO-), and it is more preferable that both are carbonyl bonds (-CO-).

[0246] In general formula (24), R4 represents an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, amino group, nitro group, etc. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, decyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, and cyclohexylmethyl group. Among these, the ethyl group, propyl group, and isopropyl group are preferred.

[0247] In general formula (24), R5 and R6 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heterocycle having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, amino group, nitro group, etc. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, and cyclohexylmethyl group. Among these, pentyl group, hexyl group, heptyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, and cyclohexylmethyl group are preferred. Examples of heterocyclic groups having 2 to 30 carbon atoms include pyridyl, pyrimidyl, furyl, tetrahydrofuryl, dioxolanyl, imidazolidyl, oxazolidyl, piperidyl, and morpholinyl groups. Examples of aryl groups having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and anthuryl groups, and may also be aryl groups substituted with halogen atoms, amino groups, nitro groups, etc. Examples of arylalkyl groups having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl groups, and may also be arylalkyl groups substituted with halogen atoms, amino groups, nitro groups, etc.

[0248] Among these, R5 and R6 are more preferably linear alkyl groups having 1 to 20 carbon atoms and cyclic alkyl groups having 1 to 20 carbon atoms.

[0249] In general formula (24), R7 and R8 each independently represent an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof, and may also be an alkyl group substituted with a halogen atom, amino group, nitro group, etc. Examples include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, cyclopentyl group, cyclopentylmethyl group, and cyclohexyl group. Among these, methyl group, ethyl group, propyl group, and isopropyl group are preferred from the viewpoint of reactivity. Examples of heterocyclic groups having 2 to 30 carbon atoms include pyridyl, pyrimidyl, furyl, tetrahydrofuryl, dioxolanyl, imidazolidyl, oxazolidyl, piperidyl, and morpholinyl groups. Examples of aryl groups having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, and anthuryl groups, and may also be aryl groups substituted with halogen atoms, amino groups, nitro groups, etc. Among these, the phenyl group is preferred from the viewpoint of reactivity. Examples of arylalkyl groups having 7 to 30 carbon atoms include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl groups, and may also be arylalkyl groups substituted with halogen atoms, amino groups, nitro groups, etc.

[0250] Among these, R7 and R8 are preferably methyl, ethyl, or phenyl groups from the viewpoint of reactivity, with methyl or ethyl groups being more preferred.

[0251] The method for producing the compound represented by general formula (24) is not particularly limited, and known methods can be used. For example, the method described in Japanese Patent Publication No. 2017-523465 can be used.

[0252] Specific examples of compounds represented by general formula (24) are shown. However, the present invention is not limited to these.

[0253] [ka]

[0254] Examples of thermal polymerization initiators include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane. Pinacol compounds such as 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tert-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, and 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2-tetraphenylethane; Azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonnitrile), 2,2'-azobis[N-(2-propenyl)2-methylpropionamide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); Examples include organic peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, succinic acid peroxide, and benzoyl peroxide. Among these, pinacol compounds are preferred.

[0255] Polymerization initiator (D) can be used alone or in combination of two or more types.

[0256] The polymerization initiator (D) content is preferably 0.5 to 20% by mass of 100% by mass of the non-volatile content of the composition.

[0257] [Coloring agent (E)] The composition of the present invention may contain a coloring agent (E). This allows for control of the transmittance in the visible light region of the optical filter.

[0258] Colorants (E) include pigments and dyes. Among these, pigments are preferred from the viewpoint of lightfastness, heat resistance, and solvent resistance.

[0259] (Pigment) The pigment is preferably a compound classified as a pigment in the color index. Red pigments include, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179 ,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259, Examples include pigments 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, pigments described in Japanese Patent Publication No. 2014-134712, pigments described in Japanese Patent Publication No. 6368844, and the like. Among these, from the viewpoint of heat resistance, light resistance, and transmittance, CI Pigment Red 48:1,122,177,224,242,269,254,291,295,296, the pigment described in Japanese Patent Publication No. 2014-134712, and the pigment described in Japanese Patent Publication No. 6368844 are preferred, and CI Pigment Red 177,254,291,295,296, the pigment described in Japanese Patent Publication No. 2014-134712, and the pigment described in Japanese Patent Publication No. 6368844 are even more preferred.

[0260] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0261] Yellow pigments include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 15 Examples include pigments described in 1,152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, Japanese Patent Publication No. 2012-226110, Japanese Patent Publication No. 2017-171912, Japanese Patent Publication No. 2017-171913, Japanese Patent Publication No. 2017-171914, Japanese Patent Publication No. 2017-171915, etc. Among these, the pigments described in CI Pigment Yellow 138, 139, 150, 185, 231, 233 and Japanese Patent Publication No. 2012-226110 are preferred.

[0262] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63. Among these, CI Pigment Green 36, 58, 59, 62, and 63 are preferred.

[0263] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

[0264] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, CI Pigment Violet 19 and 23 are preferred.

[0265] Examples of black pigments include CI Pigment Black 1, 6, 7, 12, 20, 31, 32, etc. Compounds described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No. 2012-515234, Japanese Patent Publication No. Hei 1-170601, Japanese Patent Publication No. Hei 2-34664, etc. are also examples.

[0266] Inorganic pigments can also be used as the coloring agent (E). Examples of inorganic pigments include titanium dioxide, barium sulfate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black.

[0267] (dye) Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Derivatives of these dyes, as well as lake pigments (dyes obtained by lake formation), are also examples.

[0268] Acid dyes preferably have acidic groups such as sulfonic acid or carboxylic acid. Salt compounds are also preferred, which are salts of acid dyes with nitrogen-containing compounds such as quaternary ammonium salts, tertiary amines, secondary amines, or primary amines. Salt compounds are also preferred, which are salts of resin components having these functional groups with acid dyes. Furthermore, salt compounds can be easily modified into sulfonamide compounds by sulfonamidation to obtain curable compositions with excellent resistance (lightfastness, solvent resistance). Furthermore, salt-forming compounds of acid dyes and compounds containing an onium base are also preferred due to their excellent resistance (light resistance and solvent resistance). The compound containing the onium base is preferably a resin having a cationic group.

[0269] Basic dyes can be used as is, but salt-forming compounds that form salts with organic acids, perchloric acid, or their metal salts are preferred. Salt-forming compounds of basic dyes are preferred because they have excellent resistance (lightfastness, solvent resistance) and affinity with pigments. Furthermore, in salt-forming compounds of basic dyes, preferred anionic components that act as counterions are salt-forming compounds obtained by salting with organic sulfonic acids, organic sulfuric acids, fluorine-containing phosphorus anionic compounds, fluorine-containing boron anionic compounds, cyano-containing nitrogen anionic compounds, anionic compounds having a conjugate base of an organic acid having a halogenated hydrocarbon group, and acid dyes. Note that the resistance of the salt-forming compound is further improved if it contains polymerizable unsaturated groups in its molecule.

[0270] The chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), and azite dyes. Examples of dye structures derived from dyes selected from chloromethic acid dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

[0271] Among these, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, a pigment structure derived from a pigment selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferred, and a pigment structure derived from a pigment selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, and phthalocyanine dyes is more preferred.

[0272] The coloring agent (E) can be used alone or in combination of two or more types.

[0273] The content of the coloring agent (E) is preferably 5% by mass or less, and more preferably 0.5 to 3% by mass, based on 100% by mass of the nonvolatile content of the curable composition.

[0274] (Fine-graining of organic pigments) Organic pigments are preferably used after being finely milled. The milling method is not particularly limited, and for example, wet milling, dry milling, or dissolution milling can all be used. Among these, salt milling by the kneader method, which is a type of wet milling, is preferred. The average primary particle size of the finely milled pigment, as determined by TEM (transmission electron microscopy), is preferably 5 to 90 nm. However, from the viewpoint of dispersibility and contrast ratio, an average primary particle size of 10 to 70 nm is more preferable.

[0275] Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while heated using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, etc., and then washed with water to remove the water-soluble inorganic salt and water-soluble organic solvent. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain pigments with a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

[0276] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate, with sodium chloride (table salt) being preferred from a cost standpoint. The amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, and more preferably 300 to 1,000 parts by mass, per 100 parts by mass of pigment, considering both processing efficiency and production efficiency.

[0277] The water-soluble organic solvent serves to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is prone to evaporation, a high-boiling-point solvent with a boiling point of 120°C or higher is preferred from a safety standpoint. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The amount of water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, and more preferably 50 to 500 parts by mass, per 100 parts by mass of pigment.

[0278] A resin may be added to the salt milling process as needed. The type of resin is not particularly limited and includes natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature, insoluble in water, and partially soluble in the organic solvent. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of pigment.

[0279] [Leveling agent (F)] The composition of the present invention may contain a leveling agent (F). This further improves the wettability and drying properties of the substrate during coating.

[0280] Examples of leveling agents (F) include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0281] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0282] Examples of commercially available silicone-based surfactants include BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 from Bic Chemie, and FZ-70 from Toray Dow Corning. Examples include 02, 2110, 2122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

[0283] Examples of fluorinated surfactants include compounds having fluorocarbon chains.

[0284] Examples of commercially available fluorine-based surfactants include Surflon S-242, 243, 420, 611, 651, and 386 from AGC Seimi Chemical Co., Ltd., Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, as well as R-40-LM, R-41, RS-72-K, and DS-21 from DIC Corporation, FC-4430 and 4432 from Sumitomo 3M Corporation, EF-PP31N09, EF-PP33G1, and EF-PP32C1 from Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A from Neos Corporation.

[0285] Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristelle ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate Examples include sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkylimidazoline, etc.

[0286] Examples of commercially available nonionic surfactants include Kao's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L1 20, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amito 1 Examples include 02, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA's Adekapluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, and Kyoeisha Chemical's (meth)acrylic acid-based (co)polymer Polyflow-No.75, No.90, No.95.

[0287] Cationic surfactants include, for example, alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

[0288] Examples of commercially available cationic surfactants include Kao Corporation's Acetamine 24, Cotamine 24P, 60W, and 86P Concentrate.

[0289] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate esters.

[0290] Examples of commercially available anionic surfactants include Neos's Futergent 100 and 150, and ADEKA's Adekahope YES-25, Adekacol TS-230E, PS-440E, and EC-8600.

[0291] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

[0292] Examples of commercially available amphoteric surfactants include Kao Corporation's Anchitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N.

[0293] Leveling agent (F) can be used alone or in combination of two or more types.

[0294] The leveling agent (F) content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on 100% by mass of the non-volatile content of the composition. Including an appropriate amount further improves the balance between the coating properties and adhesion of the composition.

[0295] [Organic solvent (G)] The composition of the present invention may contain an organic solvent (G).

[0296] The organic solvent (G) is not particularly limited, and known compounds can be used. For example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methyl Butyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl Benzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone,Examples include dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, etc.

[0297] Organic solvent (G) can be used alone or in combination of two or more types.

[0298] The amount of organic solvent (G) is preferably such that the non-volatile content of the composition is 5 to 50% by mass.

[0299] [Other ingredients] The composition of the present invention may contain other components not listed above. Examples of other components include sensitizers, curing agents, curing accelerators, acid generators, curing catalysts, dye derivatives, chain transfer agents, polymerization inhibitors, antioxidants, and ultraviolet absorbers. The content of these other components can be appropriately set within a range that does not impair the effects of the present invention.

[0300] [Water content] From the viewpoint of suppressing foreign matter, it is preferable that the composition of the present invention contains 2.0% by mass or less of water.

[0301] The water content in the composition is more preferably 1.5% by mass or less, and particularly preferably 1.0% by mass or less. Furthermore, the lower limit of the water content is preferable as much as possible, but there are no particular restrictions.

[0302] There are no particular restrictions on the method for controlling the water content, and known methods can be used. For example, each of the above-mentioned components can be thoroughly dried to reduce the amount of water contained in the components before use. Other methods include manufacturing the composition while blowing in dry air, an inert gas, or a mixture thereof, or adding molecular sieves after manufacturing to dehydrate the mixture.

[0303] The water content can be measured by known methods such as the Karl Fischer method.

[0304] [Method for producing the composition] The composition of the present invention can be prepared by mixing the above-mentioned components. During preparation, the components may be blended all at once, or they may be dissolved or dispersed in an organic solvent and then blended sequentially. If the solubility of the near-infrared absorbing compound in the organic solvent is low, from the viewpoint of suppressing foreign matter, it is preferable to add the near-infrared absorbing compound (A), resin (B), and organic solvent (G), etc., and perform a dispersion treatment. Then, if necessary, the composition can be produced by blending and mixing the resin (B), curable compound (C), polymerization initiator (D), and organic solvent (G), etc. The timing of blending each component is arbitrary. Furthermore, the dispersion treatment can be performed multiple times.

[0305] Examples of distributed processing machines include two-roll mills, three-roll mills, ball mills, horizontal sand mills, vertical sand mills, annular bead mills, or attritors.

[0306] When the near-infrared absorbing compound (A) is a pigment, the average dispersed particle size (secondary particle size) of the near-infrared absorbing compound (A) in the composition is preferably 30 to 200 nm, and more preferably 40 to 200 nm. A composition with a suitable particle size is more likely to be obtained with high dispersion stability.

[0307] The method for measuring the average dispersed particle diameter (secondary particle diameter) uses, for example, Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power-spectrum method), with particle permeability set to absorption mode, particle shape to non-spherical, and D50 particle diameter as the average diameter. The diluent solvent used for measurement is the same organic solvent used for dispersion, and it is preferable to measure immediately after sample preparation of ultrasonically treated samples to obtain results with less variation.

[0308] The composition is preferably subjected to centrifugation, sintering filter filtration or membrane filter filtration to remove coarse particles of 5 μm or larger, preferably coarse particles of 1 μm or larger, more preferably coarse particles of 0.5 μm or larger, and any mixed dust. The composition of the present invention preferably contains substantially no particles of 0.5 μm or larger, and more preferably contains no particles of 0.3 μm or smaller.

[0309] <Membrane> The film of the present invention is formed using the above-described composition. The film may be used in a laminated state on a substrate, or the film may be peeled off from the substrate. Furthermore, the film may be a flat film or a film with a pattern formed thereon.

[0310] [Memory manufacturing method] The method for manufacturing the film is not particularly limited, and known methods can be used. For example, it can be manufactured by a process of coating the composition of the present invention onto a substrate.

[0311] Examples of substrates include glass substrates, resin substrates, and silicon substrates. Examples of resin substrates include polycarbonate substrates, polyester substrates, aromatic polyamide substrates, polyamide-imide substrates, and polyimide substrates. An organic light-emitting layer may be formed on these substrates. For example, an image sensor such as a CCD or CMOS may be formed on the surface of a silicon substrate. In addition, a primer layer may be provided on the substrate as needed to improve adhesion with the upper layer, prevent diffusion of materials, and flatten the substrate surface.

[0312] A known coating method can be used. Examples include the drop method, slit coating method, spray method, roll coating method, rotary coating method, casting coating method, inkjet method, flexographic printing, screen printing, gravure printing, and offset printing.

[0313] The film thickness can be adjusted as appropriate depending on the purpose. A film thickness of 0.05 to 20.0 μm is preferred, and 0.3 to 10.0 μm is more preferred.

[0314] The layer formed by the coating process is dried. The drying temperature is preferably, for example, 80 to 240°C. The drying time is preferably 2 minutes to 2 hours.

[0315] Furthermore, the manufacturing of the film may include a step of forming a pattern. Methods for forming the pattern include photolithography and dry etching. However, if the film is to be used as a flat film, the pattern formation step may not be necessary.

[0316] The manufacturing method for forming patterns will be described in detail below.

[0317] (When forming a pattern using photolithography) When forming a pattern using photolithography, the layer formed by coating the substrate with the composition of the present invention is dried as needed (pre-bake), then exposed in a patterned manner through a mask (exposure step), the unexposed areas are removed by alkaline development (development step), and then the pattern is heat-treated as needed (post-bake step).

[0318] [Exposure process] The exposure process involves exposing a layer formed by coating to a specific pattern via a mask using an exposure device such as a stepper. This allows the exposed area to harden. Examples of active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF rays (wavelength 193 nm). Furthermore, exposure may be performed by continuously irradiating with light, or by repeatedly irradiating and pausing with light in short cycles (for example, at the millisecond level or less) (pulsed exposure).

[0319] [Development process] Next, by performing an alkaline development treatment, the unexposed layers dissolve in the alkaline aqueous solution, leaving only the hardened parts and obtaining a patterned film. Examples of alkaline developers include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, and more preferably 11.5 to 12.5. Using an appropriate pH suppresses pattern roughness and peeling, and improves the residual film rate after development. Development methods include, for example, the dip method, spray method, and paddle method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

[0320] [Post-baking process] After development, heat treatment (post-baking) can be performed as needed. Post-baking improves the durability of the film. The temperature is preferably between 80 and 300°C. The duration is preferably between 2 minutes and 1 hour. When a material with low heat resistance is used as the substrate, or when an organic electroluminescent element is used as the light source, the temperature is preferably 150°C or lower, and more preferably 130°C or lower.

[0321] (When forming a pattern using the dry etching method) When forming a pattern by dry etching, for example, a layer formed by coating a substrate with the composition of the present invention is heated and cured. Next, a patterned photoresist layer is formed on the cured film, and then dry etching is performed on the cured film using an etching gas, with the patterned photoresist layer as a mask. For pattern formation by dry etching, the method described in Japanese Patent Application Publication No. 2013-064993 can be referenced.

[0322] <Optical filters> The film of the present invention can be used in optical filters. Preferred optical filters include, for example, infrared cut filters and infrared transmission filters. The optical filters of the present invention can be manufactured in the same manner as the film described above.

[0323] <Image display device> The film of the present invention can be used in image display devices. Examples of image display devices include liquid crystal displays and organic EL displays. The form in which it is used in image display devices is not particularly limited, but it can be used as a color filter, black matrix, light-shielding filter, infrared cut filter, or infrared transmission filter. The form used in the image display device is not particularly limited, as long as it functions as an image display device. For example, the configuration described in "Next-Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994) is one such example. For definitions of image display devices and details of various image display devices, see, for example, "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Junsho Ibuki, Sangyo Tosho Co., Ltd., published in 1989).

[0324] <Solid-state image sensor> The film of the present invention can be used in solid-state image sensors. The form in which it is used in solid-state image sensors is not particularly limited, but for example, it may have a substrate on which there are multiple photodiodes constituting the light-receiving area of ​​a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like, a light-shielding film on which only the light-receiving portion of the photodiode is open, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and a filter on the device protection film. Furthermore, it may have a configuration in which a light-gathering means (e.g., a microlens, etc.; the same applies hereinafter) is provided on the device protection film below the filter (closer to the substrate), or a configuration in which the light-gathering means is provided on the filter. The filter may also have a structure in which a hardened film forming each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partitions. In this case, it is preferable that the partitions have a low refractive index with respect to each colored pixel. The imaging device equipped with the solid-state image sensor of the present invention can be used in a variety of applications, such as digital cameras, electronic devices with imaging functions (smartphones, tablet terminals, etc.), in-vehicle cameras, surveillance cameras, and optical sensors.

[0325] <Infrared sensor> The film of the present invention can be used in an infrared sensor. The form in which it is used in an infrared sensor is not particularly limited. Figure 1 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor equipped with the film of the present invention. The infrared sensor shown in Figure 1 comprises a 100 and a solid-state image sensor 110.

[0326] The imaging area on the solid-state image sensor 110 is formed by combining an infrared cut filter 111 and a color filter 112.

[0327] The infrared cut filter 111 can be formed using the composition of the present invention, and transmits light in the visible light region (e.g., light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (e.g., light with a wavelength of 800 to 1,300 nm).

[0328] The color filter 112 is a color filter in which pixels that transmit and absorb light of specific wavelengths in the visible light region are formed. For example, a color filter in which red (R), green (G), and blue (B) pixels are formed is used.

[0329] Between the infrared transmission filter 113 and the solid-state image sensor 110, a resin film 114 is placed that can transmit light of wavelengths that have passed through the infrared transmission filter 113.

[0330] The infrared transmission filter 113 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength. Preferably, the infrared transmission filter 113 shields light with wavelengths of 400 to 830 nm and transmits light with wavelengths of 900 to 1,300 nm.

[0331] A microlens 115 is positioned on the incident light h side of the color filter 112 and the infrared transmission filter 113. A planarization film 116 is formed to cover the microlens 115.

[0332] In the configuration shown in Figure 1, a resin film 114 is arranged, but an infrared transmission filter 113 may be formed instead of the resin film 114.

[0333] This infrared sensor can simultaneously capture image information, enabling motion sensing and other applications that recognize moving objects. Furthermore, because it can acquire distance information, it can capture images containing 3D data. In addition, this infrared sensor can also be used as a biometric authentication sensor. [Examples]

[0334] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" refers to "parts by mass" and "%" refers to "mass percent". In the present invention, nonvolatile content or nonvolatile content concentration refers to the mass residue after standing in an oven at 230°C for 30 minutes.

[0335] Prior to the examples, each measurement method will be described.

[0336] (Average molecular weight of resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with a radioisotope detector. An HLC-8220GPC (Tosoh Corporation) was used, with two separation columns connected in series. Both columns were packed with two TSK-GEL SUPER HZM-N columns. Measurements were performed at an oven temperature of 40°C, using tetrahydrofuran (THF) solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. Molecular weights are expressed on a polystyrene basis.

[0337] (Acid value of resin) 0.5 to 1 g of resin solution was mixed with 80 ml of acetone and 10 ml of water and stirred to dissolve uniformly. A 0.1 mol / L aqueous KOH solution was used as the titrant, and the solution was titrated using an automatic titrator ("COM-555," manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mg KOH / g). The acid value per unit of non-volatile content of the resin was then calculated from the acid value of the resin solution and the concentration of non-volatile content of the resin solution.

[0338] (Amine value of resin) The amine value of the resin is calculated by converting the total amine value (mgKOH / g), which was measured according to the ASTM D 2074 method, into a non-volatile content value.

[0339] <Manufacturing of near-infrared absorbing compound (A)> (Compound represented by general formula (1) (A1-1)) In a reaction vessel, 26 parts phthalonitrile, 143 parts 2,3-dicyanonaphthalene, 890 parts n-amyl alcohol, 137 parts DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene), and 34 parts aluminum trichloride were mixed and stirred, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution, which was cooled to 30°C while stirring, was poured into a mixed solvent consisting of 5,000 parts methanol and 10,000 parts deionized water while stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2,000 parts methanol and 4,000 parts deionized water, and dried to obtain compound a. Next, 140 parts of compound a were added to 1,500 parts of concentrated sulfuric acid in a reaction vessel under ice bath conditions, and the mixture was stirred for 1 hour. Subsequently, 1,000 parts of 3°C cold water were poured into this sulfuric acid solution, and the resulting precipitate was filtered, washed with water, washed with a 2.5% sodium hydroxide aqueous solution, washed with water, dried, and compound b was obtained. 5 parts diphenyl phosphate was added to 200 parts N-methylpyrrolidone and thoroughly mixed, then heated to 50°C. 10 parts compound b was added little by little to this solution, and the mixture was stirred at 90°C for 120 minutes. The endpoint of the reaction was identified, for example, by dropping the reaction solution onto filter paper until the seepage stopped. Subsequently, 2,000 parts of deionized water were added to this reaction solution, and the resulting precipitate was filtered, washed with water, and dried to obtain a mixture of compounds represented by the following chemical formula (25) (mixing ratio: n1:n2:n3:n4 = 7:19:59:15) (maximum absorption wavelength: 765 nm). Fifty parts of the compound represented by the obtained chemical formula (25), 500 parts of sodium chloride, and 60 parts of diethylene glycol were placed in a stainless steel gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 12 hours. Next, the kneaded mixture was added to warm water and stirred for 1 hour while heating to approximately 80°C to form a slurry. After filtering and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight and then pulverized to finely grind the mixture.

[0340] Chemical formula (25) [ka]

[0341] (Compounds represented by general formula (1) (A1-2)) In a reaction vessel, 178 parts of 2,3-dicyanonaphthalene, 890 parts of n-amyl alcohol, 137 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene), and 40 parts of anhydrous aluminum chloride were mixed and stirred, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and then injected with stirring into a mixed solvent consisting of 5,000 parts methanol and 10,000 parts water to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2,000 parts methanol and 4,000 parts water, and dried to obtain compound c. Next, 10 parts of compound c were added to 100 parts of concentrated sulfuric acid in a reaction vessel under ice bath conditions, and the mixture was stirred for 1 hour. Subsequently, 1,000 parts of this sulfuric acid solution were poured into 3°C cold water, and the resulting precipitate was filtered, washed with water, washed with a 2.5% sodium hydroxide aqueous solution, washed with water, and dried to obtain compound d. 5 parts diphenyl phosphate was added to 200 parts N-methylpyrrolidone and thoroughly stirred, then heated to 50°C. 10 parts compound d was added little by little to this solution, and the mixture was stirred at 90°C for 120 minutes. The endpoint of the reaction was identified, for example, by dropping the reaction solution onto filter paper until the seepage stopped. Subsequently, 2,000 parts of deionized water were added to this reaction solution, and the resulting precipitate was filtered, washed with water, and dried to obtain the compound represented by the following chemical formula (26) (maximum absorption wavelength: 740 nm). Fifty parts of the compound represented by the obtained chemical formula (26), 500 parts of sodium chloride, and 60 parts of diethylene glycol were placed in a stainless steel gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 12 hours. Next, the kneaded mixture was added to warm water and stirred for 1 hour while heating to approximately 80°C to form a slurry. After filtering and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight and then pulverized to finely grind the mixture.

[0342] Chemical formula (26) [ka]

[0343] (Compounds represented by general formula (1) (A1-3)) In a reaction vessel, 26 parts phthalonitrile, 143 parts 2,3-dicyanonaphthalene, 890 parts n-amyl alcohol, 137 parts DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene), and 34 parts aluminum trichloride were mixed and stirred, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution, which was cooled to 30°C while stirring, was poured into a mixed solvent consisting of 5,000 parts methanol and 10,000 parts deionized water while stirring to obtain a blue slurry. This slurry was filtered, washed with a mixed solvent consisting of 2,000 parts methanol and 4,000 parts deionized water, and dried to obtain compound e. Next, 140 parts of compound e were added to 1,500 parts of concentrated sulfuric acid in a reaction vessel under ice bath conditions, and the mixture was stirred for 1 hour. Subsequently, 1,000 parts of this sulfuric acid solution were poured into 3°C cold water, and the resulting precipitate was filtered, washed with water, washed with a 2.5% sodium hydroxide aqueous solution, washed with water, dried, and a mixture of compounds represented by the following chemical formula (27) was obtained (mixing ratio: n1:n2:n3:n4 = 7:19:59:15) (maximum absorption wavelength: 735 nm). Fifty parts of the compound represented by the obtained chemical formula (27), 500 parts of sodium chloride, and 60 parts of diethylene glycol were placed in a stainless steel gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 12 hours. Next, the kneaded mixture was added to warm water and stirred for 1 hour while heating to approximately 80°C to form a slurry. After filtering and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight and then ground to finely pulverize it.

[0344] Chemical formula (27) [ka]

[0345] (Compound (A2-1)) 400 parts toluene, 40.0 parts 1,8-diaminonaphthalene, 32.2 parts 3,5-dimethylcyclohexanone, and 0.087 parts p-toluenesulfonic acid monohydrate were mixed and heated and stirred under a nitrogen atmosphere under reflux for 3 hours. Water produced during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was complete, the toluene was distilled to obtain a dark brown solid, which was extracted with acetone and purified by recrystallization in a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts toluene and 160 parts n-butanol, and 13.8 parts 3,4-dihydroxy-3-cyclobutene-1,2-dione were added. The mixture was heated and stirred under a nitrogen atmosphere under reflux for 8 hours. Water produced during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was complete, the solvent was distilled, and 200 parts of hexane were added to the resulting reaction mixture while stirring. The resulting dark brown precipitate was filtered off, and then washed sequentially with hexane, ethanol, and acetone. The mixture was dried under reduced pressure to obtain the compound represented by the following chemical formula (28) (maximum absorption wavelength: 740 nm). Fifty parts of the compound represented by the obtained chemical formula (28), 500 parts of sodium chloride, and 60 parts of diethylene glycol were placed in a stainless steel gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 12 hours. Next, the kneaded mixture was added to warm water and stirred for 1 hour while heating to approximately 80°C to form a slurry. After filtering and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight and then pulverized to finely grind the mixture.

[0346] Chemical formula (28) [ka]

[0347] (Compound (A2-2)) In accordance with the description in National Publication No. 2017 / 002920, a compound represented by the following chemical formula (29) was obtained (maximum absorption wavelength: 792 nm).

[0348] Chemical formula (29) [ka]

[0349] (Compound (A2-3)) Following the description in International Publication No. 2006 / 006573, a compound represented by the following chemical formula (30) was obtained (maximum absorption wavelength: 845 nm).

[0350] Chemical formula (30) [ka]

[0351] (Compound (A2-4)) Following the description in International Publication No. 2019 / 058882, a compound represented by the following chemical formula (31) was obtained (maximum absorption wavelength: 783 nm).

[0352] Chemical formula (31) [ka]

[0353] (Compound (A2-5)) In accordance with the description in Japanese Patent Publication No. 2016-079331, a compound represented by the following chemical formula (32) was obtained (maximum absorption wavelength: 854 nm).

[0354] Chemical formula (32) [ka]

[0355] (Compound (A2-6)) In a reaction vessel, 10.7 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. Then, 95.2 parts of a 1 mol / 1 toluene solution of titanium tetrachloride was added dropwise. After the dropwise addition, 10.0 parts of indigo were added and the mixture was refluxed for 10 hours. After the reaction was complete, methanol was added, and the mixture was filtered to obtain a green powder. This was separated from the green powder with dichloromethane and water, and the organic layer was concentrated to obtain 14.6 parts of compound d. In a reaction vessel, 13.5 parts of compound d, 9.0 parts of bis(2,4-pentanedionato)zinc(II), and 120 parts of tetrahydrofuran were mixed and stirred, and the mixture was heated and stirred at 40°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and then poured into 500 parts of methanol while stirring to obtain a blue slurry. This slurry was filtered, washed with 500 parts of methanol, washed with 500 parts of water, and dried to obtain a mixture of compounds represented by the following chemical formula (33) (mixing ratio: dimer:trimer:tetramer = 81:17:2, maximum absorption wavelength: 735 nm). Fifty parts of the compound represented by the obtained chemical formula (33), 500 parts of sodium chloride, and 60 parts of diethylene glycol were placed in a stainless steel gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 12 hours. Next, the kneaded mixture was added to warm water and stirred for 1 hour while heating to approximately 80°C to form a slurry. After filtering and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight and then pulverized to finely grind the mixture.

[0356] Chemical formula (33) [ka]

[0357] (Compound (A2-7)) In accordance with the description in Japanese Patent Publication No. 2021-47216, a compound represented by the following chemical formula (34) was obtained (maximum absorption wavelength: 734 nm).

[0358] Chemical formula (34) [ka]

[0359] <Manufacturing of resin (B)> (Resin (B1-1) solution) In a reactor equipped with a gas inlet pipe, condenser, stirring blades, and thermometer, 40 parts methyl methacrylate, 10 parts n-butyl methacrylate, and 13.2 parts tetramethylethylenediamine as a catalyst were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, thereby purging the system with nitrogen. Next, 9.3 parts ethyl bromoisobutyrate as an initiator, 5.6 parts cuprous chloride as a catalyst, and 100 parts propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) were charged, and the temperature was raised to 110°C under a nitrogen flow to start polymerization of the first block (block B). After 4 hours of polymerization, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or higher based on the non-volatile content. Next, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as the second block (block A) monomer, and 10 parts of methacryloyloxyethyl benzyldimethylammonium chloride were added to the reaction apparatus. The reaction was continued by stirring while maintaining a temperature of 110°C and a nitrogen atmosphere. Two hours after the addition of the compounds, the polymerization solution was sampled and the non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate of the second block (block A) was 98% or higher, and the reaction solution was cooled to room temperature to stop the polymerization. After cooling to room temperature, approximately 2 g was sampled and heated and dried at 180°C for 20 minutes, and the non-volatile content was measured. PGMAc was added to the solution so that the non-volatile content was 30% by mass, and a resin solution (B1-1) with a basic group in the block structure was prepared. The amine value was 169.8 mg KOH / g.

[0360] (Resin (B1-2) solution) In a reactor equipped with a gas inlet pipe, condenser, stirring blades, and thermometer, 30 parts methyl methacrylate, 30 parts n-butyl methacrylate, 20 parts hydroxyethyl methacrylate, and 13.2 parts tetramethylethylenediamine were charged. The mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was purged with nitrogen. Next, 9.3 parts ethyl bromoisobutyrate, 5.6 parts cuprous chloride, and 133 parts PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to start polymerization of the first block (block B). After 4 hours of polymerization, the polymerization solution was sampled and the non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate was 98% or higher. Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Funcryl FA-711MM) were added to the reactor as the monomer for the second block (block A). The reaction was continued by stirring while maintaining a temperature of 110°C and a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, the polymerization solution was sampled and the non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate of the second block (block A) was 98% or higher, and the reaction solution was cooled to room temperature to stop the polymerization. PGMAc was added to the solution so that the non-volatile content was 30% by mass to prepare a resin solution (B1-2) having basic groups in the block structure. The amine value was 57 mgKOH / g.

[0361] (Resin (B1-3) solution) A resin with the structure described below, as described in International Publication No. 2019 / 058882, was used to prepare a resin solution (B1-3) having randomly structured basic groups by adding PGMAc to the resin so that the non-volatile content was 30% by mass. The amine value was 45 mgKOH / g and the acid value was 32.3 mgKOH / g. [ka]

[0362] (Resin (B2-1) solution) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet tube, and stirrer into a separable four-neck flask. 100 parts of PGMAc were placed in this vessel, and while injecting nitrogen gas into the vessel, it was heated to 120°C. At the same temperature, a mixture of 85.29 parts glycidyl methacrylate, 66.01 parts dicyclopentanyl methacrylate, and 10.42 parts styrene, along with a polymerization initiator (0.5 parts azobisisobutyronitrile dissolved in PGMAc), was added dropwise over 2.5 hours to carry out the polymerization reaction. Next, the flask was purged with air, and 43.24 parts acrylic acid, 0.3 parts trisdimethylaminomethylphenol, and 0.3 parts hydroquinone were added and the mixture was reacted at 120°C for 5 hours. This caused the epoxy group of glycidyl methacrylate to react with the carboxyl group of acrylic acid. Furthermore, 52.64 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added and the mixture was reacted at 120°C for 4 hours. This caused an esterification reaction between the hydroxyl groups generated by glycidyl methacrylate and acrylic acid and the tetrahydrophthalic anhydride. Subsequently, PGMAc was added to achieve a non-volatile content of 20% by mass to prepare the resin (B2-1) solution. The weight-average molecular weight (Mw) was 30,000, and the acid value was 77 mgKOH / g.

[0363] (Resin (B2-2) solution) 160 parts of PGMAc were placed in a reaction vessel, which was a separable four-neck flask fitted with a thermometer, condenser, nitrogen gas inlet tube, and stirrer. The vessel was heated to 120°C while nitrogen gas was injected into it. At the same temperature, 70.3 parts of benzyl methacrylate, 15.5 parts of methacrylic acid, 14.2 parts of dicyclopentanyl methacrylate, 3.6 parts of the polymerization initiator azobisisobutyronitrile, and a mixture of PGMAc were added dropwise over 2.5 hours using a dropping tube. After the dropwise addition was complete, the mixture was stirred at 120°C for a further 2 hours. Then, PGMAc was added to prepare the resin (B2-2) solution so that the non-volatile content was 20% by mass. The weight-average molecular weight was 8,000 and the acid value was 85 mgKOH / g.

[0364] (Resin (B2-3) solution) 3.26 parts of PGMAc were heated to 85°C under a nitrogen stream. While stirring this solution, a mixed solution of 22.36 parts of glycidyl methacrylate, 12.38 parts of 1,1,1,3,3,3-hexafluoroisopropyl methacrylate, 13.26 parts of cyclohexanone, and 1.45 parts of 2,2'-azobisisobutyrate was added dropwise over 2 hours. After the addition was complete, the mixture was stirred for a further 2 hours at 85°C and then for a further 2 hours at 90°C. Subsequently, PGMAc was added to obtain resin (B2-3) with a non-volatile content of 20% by mass. The weight-average molecular weight (Mw) was 13,300.

[0365] (Resin (B2-4) solution) 100 parts of 8-methyl-8-methoxycarbonyltetracyclo[4.4.0.12,5.17,10]dodeca-3-ene, 18 parts of 1-hexene, and 300 parts of toluene were charged into a nitrogen-purged reaction vessel, and this solution was heated to 80°C. Next, 0.2 parts of a toluene solution of triethylaluminum and 0.9 parts of a toluene solution of methanol-modified tungsten hexachloride were added to the solution in the reaction vessel as polymerization catalysts, and this solution was heated and stirred at 80°C for 3 hours to carry out a ring-opening polymerization reaction and obtain a ring-opened polymer solution. 1,000 parts of the obtained ring-opening polymer solution were placed in an autoclave, and 0.12 parts of RuHCl(CO)[P(C6H5)3]3 were added to the ring-opening polymer solution, and a hydrogen gas pressure of 100 kg / cm² was applied. 2 The hydrogenation reaction was carried out by heating and stirring at a reaction temperature of 165°C for 3 hours. After cooling the resulting reaction solution, the hydrogen gas was released. This reaction solution was poured into a large amount of methanol to separate and recover the solidified material, which was then dried. Subsequently, methylene chloride was added to prepare a resin (B2-4) solution so that the non-volatile content was 20% by mass. The weight-average molecular weight (Mw) was 87,000.

[0366] (Resin (B2-5) solution) Under a stream of dry nitrogen, 31.13 parts (0.085 mol; 77.3 mol% relative to the total structural units derived from the amine and its derivatives) of 2,2-bis(3-amino-4-hydroxyphenyl)hexafluoropropane, 1.24 parts (0.0050 mol; 4.5 mol% relative to the total structural units derived from the amine and its derivatives) of 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 2.18 parts (0.020 mol; 18.2 mol% relative to the total structural units derived from the amine and its derivatives) of 3-aminophenol / methaminophenol as a terminal encapsulant, and 150.00 parts of N-methyl-2-pyrrolidone (hereinafter, NMP) were weighed and dissolved in a three-necked flask. To this, a solution prepared by dissolving 31.02 parts (0.10 mol; 100 mol% relative to the total carboxylic acid and its derivatives) of bis(3,4-dicarboxyphenyl) ether dianhydride in 50.00 g of NMP was added, and the mixture was stirred at 20°C for 1 hour, followed by stirring at 50°C for 4 hours. Then, 15 parts of xylene were added, and the mixture was stirred at 150°C for 5 hours while azeotropically stirring with water. After the reaction was complete, the reaction solution was added to 3 L of water, and the precipitated solid was filtered to obtain the final product. The obtained solid was washed three times with water and then dried in a vacuum dryer at 80°C for 24 hours. Subsequently, 3-methoxy-n-butyl acetate was added to prepare the resin (B2-5) solution so that the non-volatile content was 20% by mass. The weight-average molecular weight (Mw) was 27,000.

[0367] <Production of the composition> [Example 1] (Composition 1) 2.8 parts of compound (A1-1) represented by general formula (1), 2.8 parts of compound (A2-1), 7.0 parts of resin (B1-1) solution, and 22.4 parts of organic solvent (G-1) were mixed by stirring until homogeneous. Then, using a zirconia bead with a diameter of 0.5 mm, the mixture was dispersed for 3 hours using an Eiger mill (Eiger Japan "Mini Model M-250 MKII"), and then filtered through a filter with a pore size of 1.0 μm. Next, 12.0 parts of resin (B2-1) solution, 5.0 parts of curable compound (C-1), 0.5 parts of polymerization initiator (D-1), 0.2 parts of polymerization initiator (D-2), 1.0 part of leveling agent (F), and organic solvent (G-1) were added so that the total volume of the composition was 100 parts. After stirring and mixing until homogeneous, the mixture was filtered through a 1.0 μm pore size filter to obtain composition 1.

[0368] [Examples 2-23 and Comparative Example 1] (Compositions 2-24) Compositions 2 to 24 were prepared in the same manner as in Example 1, using the components and quantities listed in Tables 1-1 to 1-3.

[0369] [Table 1-1]

[0370] [Table 1-2]

[0371] [Table 1-3]

[0372] The components listed in the table are as follows:

[0373] [Curable compound (C)] (C-1): Aronics M-305 (manufactured by Toagosei Co., Ltd., a mixture of pentaerythritol triacrylate and pentaerythritol tetraacrylate) (C-2): EHPE-3150 (manufactured by Daicel Corporation, a compound with approximately 15 epoxy groups) (C-3): Arronix M-520 (manufactured by Toagosei Co., Ltd., carboxyl group-containing polyfunctional acrylate) (C-4):X-12-1048 (manufactured by Shin-Etsu Silicone Co., Ltd., a compound containing an alkoxysilyl group)

[0374] [Polymerization initiator (D)] [ka]

[0375] (D-2): Omnirad369 (manufactured by IGM Resins) (D-4): Benzopinacol (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0376] [Leveling agent (F)] (F-1): BYK-330 (manufactured by Bic Chemie) (F-2): Megafuck F-554 (manufactured by DIC) As described above, (F-1) and (F-2) were mixed in 1 part each and dissolved in 98 parts PGMAc to form a mixed solution which was used as the leveling agent (F).

[0377] [Organic solvent (G)] (G-1): Propylene glycol monomethyl ether acetate (G-2): Methylene chloride

[0378] <Evaluation of the composition> The following evaluations were performed on the obtained compositions 1 to 24 (Examples 1 to 23 and Comparative Example 1). The evaluation results are shown in Table 2.

[0379] The obtained composition was coated onto a glass substrate using a spin coater to a dry film thickness of 1.0 μm, and then pre-baked on a hot plate at 70°C for 1 minute. Next, an illuminance of 30 mW / cm² was applied using an ultra-high pressure mercury lamp. 2 50 mJ / cm² 2 The substrate was exposed to light and then post-baked in a clean oven at 200°C for 10 minutes to obtain an evaluation substrate. In Example 21, the substrate was obtained by pre-baking and then post-baking without exposure.

[0380] [Infrared shielding performance evaluation] The obtained evaluation substrates were tested for light transmittance at wavelengths of 700-900 nm using a U-4100 spectrophotometer (Hitachi High-Technologies Corporation), and the range in which the transmittance remained continuously below 10% was determined. A value of 2 or higher was considered practical. 3: Above 100nm 2: 50nm to less than 100nm 1: Less than 50nm

[0381] [Lightfastness evaluation] The obtained evaluation substrates were subjected to a lightfastness test by irradiating them with a xenon lamp (100,000 lux) for 50 hours. Subsequently, the transmittance of light with wavelengths of 400-1,000 nm was measured, and the maximum change in transmittance before and after the lightfastness test was determined and evaluated according to the following criteria: A score of 2 or higher is considered practical. Change in transmittance (%) = |Transmittance before lightfastness test - Transmittance after lightfastness test| 3: The maximum change in transmittance is 3% or less. 2: The maximum change in transmittance exceeds 3% or is 5% or less. 1: The maximum value of the change in transmittance exceeds 5%.

[0382] [Heat resistance evaluation] The obtained evaluation substrates were heated on a hot plate at 260°C for 300 seconds to perform a heat resistance test. Subsequently, the transmittance of light with wavelengths of 400 to 1,000 nm was measured, and the maximum change in transmittance before and after the heat resistance test was determined and evaluated according to the following criteria: A score of 2 or higher is considered practical. Change in transmittance (%) = |Transmittance before heat resistance test - Transmittance after heat resistance test| 3: The maximum change in transmittance is 3% or less. 2: The maximum change in transmittance exceeds 3% or is 5% or less. 1: The maximum value of the change in transmittance exceeds 5%.

[0383] [Moisture resistance evaluation] The obtained evaluation substrates were subjected to a humidity resistance test by being left standing for 500 hours in an atmosphere of 80°C and 85% relative humidity. Afterward, the transmittance of light with wavelengths of 400 to 1,000 nm was measured, and the maximum change in transmittance before and after the humidity resistance test was determined and evaluated according to the following criteria: A score of 2 or higher is considered practical. Change in transmittance (%) = |Transmittance before moisture resistance test - Transmittance after moisture resistance test| 3: The maximum change in transmittance is 3% or less. 2: The maximum change in transmittance exceeds 3% or is 5% or less. 1: The maximum value of the change in transmittance exceeds 5%.

[0384] [Solvent resistance evaluation] The obtained evaluation substrates were immersed in cyclohexanone for 5 minutes to perform a solvent resistance test. Subsequently, the transmittance of light with wavelengths of 400 to 1,000 nm was measured, and the maximum change in transmittance before and after the solvent resistance test was determined and evaluated according to the following criteria. A score of 2 or higher is considered practical. Change in transmittance (%) = |Transmittance before solvent resistance test - Transmittance after solvent resistance test| 3: The maximum change in transmittance is 3% or less. 2: The maximum change in transmittance exceeds 3% or is 5% or less. 1: The maximum value of the change in transmittance exceeds 5%.

[0385] [Defect Assessment] The obtained composition was placed in a sealed container and stored at 40°C for one week, after which an evaluation substrate was prepared using the same method as described above. The defect density of the obtained evaluation substrate was measured using a foreign object inspection device (manufactured by KLA-Tencor). A defect is defined as a detection point with a size of 1 μm or larger. A defect density of 2 or higher is considered practical. 3:10 / cm 2 below 2:10 / cm 2 exceeding 50 / cm 2 below 1:50 / cm 2 exceed

[0386] [Table 2] [Explanation of symbols]

[0387] 100 Infrared Sensors 110 Solid-state image sensor 111 Infrared Cut Filter 112 Color Filters 113 Infrared transmission filter 114 Resin film 115 Microlenses 116 Flat membrane

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