Compound, resin composition, optical filter and solid-state imaging element

Abstract

To provide a compound having high solubility to an organic solvent, and to provide a compound which has optical characteristics suitable for manufacturing an optical filter and is excellent in heat resistance.SOLUTION: At least one compound is selected from the group consisting of a compound represented by formula (Ia) and formula (Ib).SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a compound, a resin composition, an optical filter, and a solid-state imaging device. [Background technology]

[0002] Solid-state imaging devices including optical filters that absorb near-infrared light are used in digital cameras, near-infrared sensors, and the like. Various compounds, such as compounds having a terrylene skeleton, are known as compounds for forming such optical filters. Patent Document 1 also describes a compound having a terrylene skeleton. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] International Publication No. 2017 / 070249 Summary of the Invention [Problem to be solved by the invention]

[0004] Optical filters are typically produced by dissolving the above-described compounds in a solvent together with other components such as a curable resin to prepare a curable resin composition, applying the curable resin composition to a substrate, and polymerizing it by heating at high temperatures. High solubility of each component in organic solvents such as cyclohexanone facilitates the production of optical filters, resulting in the production of uniform, high-performance optical filters. However, some compounds may not be sufficiently soluble in organic solvents, and the presence of insoluble matter has been found to significantly reduce optical performance. Furthermore, compounds used in optical filters often lack sufficient heat resistance and are therefore unable to withstand the high-temperature heating process required for producing optical filters.

[0005] Therefore, an object of the present invention is to provide a compound that is highly soluble in organic solvents and has optical properties suitable for producing optical filters and the like, as well as excellent heat resistance. [Means for solving the problem]

[0006] As a result of intensive investigations to solve the above problems, the present inventors have found that the above problems can be solved by a specific compound, and have completed the present invention. That is, the present invention includes the following aspects.

[0007] [1] At least one compound selected from the group consisting of compounds represented by formula (Ia) and formula (Ib): [ka] [In formula (Ia) and formula (Ib), R 1 ~R 4 and R 9 ~R 12 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a halogen atom, a hydroxy group or a carboxy group, and a methylene group contained in the hydrocarbon group is -O-, -CO- or -N(R B1 )- may be replaced by R 9 and R 12 , and / or R 10 and R 11 may be bonded to each other to form a ring, R A1 each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a halogen atom, a hydroxy group, a carboxy group, -OR B2 , or -COOR B2 represents n's each independently represent an integer of 1 to 5, R B1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R B2 represents a hydrocarbon group having 1 to 10 carbon atoms, V, W, X, and Y each independently represent a carbon atom or a nitrogen atom; 1 represents an aromatic heterocycle containing a nitrogen atom which may have a substituent, which is formed together with V and W, and ring Z 2 represents an aromatic heterocycle containing a nitrogen atom which may have a substituent, which is formed together with X and Y. [2] The ring Z 1 and ring Z 2 each independently represents an aromatic heterocycle containing two nitrogen atoms which may have a substituent. [3] R in the formula (Ia) and formula (Ib) 1 ~R 4 and R 9 ~R 12 represents a hydrogen atom. [4] R in the formula (Ia) and formula (Ib) A1 represents a hydrocarbon group having 1 to 10 carbon atoms. [5] A resin composition comprising at least one compound selected from the group consisting of compounds represented by formula (Ia) and formula (Ib) according to any one of [1] to [4], and an alkali-soluble resin. [6] The resin composition according to [5], further comprising a polymerizable compound and a polymerization initiator. [7] A cured product of the resin composition according to [5] or [6]. [8] An optical filter comprising the cured product according to [7]. [9] A solid-state imaging device comprising the optical filter according to [8]. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a compound that is highly soluble in organic solvents, and that has optical properties suitable for producing optical filters and the like, as well as excellent heat resistance. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, embodiments of the present invention will be described in detail. Note that the scope of the present invention is not limited to the embodiments described here, and various modifications can be made within the scope that does not impair the spirit of the present invention. Note that the multiple upper and lower limit values ​​described in this specification can be arbitrarily combined to form a suitable numerical range.

[0010] <Compound> The compound of the present invention is at least one selected from the group consisting of compounds represented by formula (Ia) and formula (Ib). [ka]

[0011] In formula (Ia) and formula (Ib), R 1 ~R 4 and R 9 ~R 12 are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a halogen atom, a hydroxy group or a carboxy group, and a methylene group contained in the hydrocarbon group is -O-, -CO- or -N(R B1 )- may be replaced by R 9 and R 12 , and / or R 10 and R 11 may be bonded to each other to form a ring.

[0012] Examples of the hydrocarbon group having 1 to 20 carbon atoms include aliphatic hydrocarbon groups and aromatic hydrocarbon groups. The aliphatic hydrocarbon group may be saturated or unsaturated, and may be linear or alicyclic.

[0013] Specific examples of saturated or unsaturated chain hydrocarbon groups include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, and icosyl groups; isopropyl, (1-ethyl)propyl, isobutyl, sec-butyl, tert-butyl, (1-ethyl)butyl, (2-ethyl)butyl, (1-propyl)butyl, isopentyl, neopentyl, tert-pentyl, (2-methyl)pentyl, (1-ethyl)pentyl, (3-ethyl)pentyl, (1-propyl)pentyl, and (1-butyl)pentyl groups. ethyl group, isohexyl group, (2-methyl)hexyl group, (5-methyl)hexyl group, (2-ethyl)hexyl group, (1-butyl)hexyl group, (1-pentyl)hexyl group, (2-methyl)heptyl group, (2-ethyl)heptyl group, (3-ethyl)heptyl group, (1-hexyl)heptyl group, (2-methyl)octyl group, (2-ethyl)octyl group, (1-heptyl)octyl group Examples of suitable alkyl groups include branched alkyl groups such as a (2-ethyl)nonyl group, a (1-octyl)nonyl group, and alkenyl groups such as a vinyl group, a 1-propenyl group, a 2-propenyl group (allyl group), a (1-methyl)ethenyl group, a 2-butenyl group, a 3-butenyl group, a 1,3-butadienyl group, a (1-(2-propenyl))ethenyl group, a (1,2-dimethyl)propenyl group, and a 2-pentenyl group. The number of carbon atoms in the saturated chain hydrocarbon group is preferably 1 to 18, more preferably 2 to 15, and even more preferably 3 to 12. The number of carbon atoms in the unsaturated chain hydrocarbon group is preferably 2 to 18, more preferably 2 to 15, and even more preferably 3 to 12.

[0014] Examples of the saturated or unsaturated alicyclic hydrocarbon group include cycloalkyl groups such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl; cycloalkenyl groups such as cyclohexenyl (e.g., cyclohex-2-ene and cyclohex-3-ene), cycloheptenyl, and cyclooctenyl; norbornyl, adamantyl, and bicyclo[2.2.2]octyl. The saturated or unsaturated alicyclic hydrocarbon group preferably has 3 to 15 carbon atoms, and more preferably 3 to 12 carbon atoms.

[0015] Examples of the aromatic hydrocarbon group include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a phenanthryl group, an anthryl group, a pyrenyl group, etc. The aromatic hydrocarbon group preferably has 6 to 15 carbon atoms, and more preferably 6 to 12 carbon atoms.

[0016] The hydrocarbon group may be a group combining two or more of the chain hydrocarbon groups, alicyclic hydrocarbon groups, and aromatic hydrocarbon groups listed above, as long as the upper limit of the carbon number is not more than 20. Such a group may be, for example, a group combining an aromatic hydrocarbon group with at least one group selected from a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group, and in such a hydrocarbon group combination, the chain hydrocarbon group may be combined as a divalent group (for example, an alkanediyl group).Examples of combined hydrocarbon groups include aralkyl groups such as benzyl, phenethyl, and 1-methyl-1-phenylethyl; arylalkenyl groups such as phenylethenyl (phenylvinyl); arylalkynyl groups such as phenylethynyl; o-tolyl, m-tolyl, p-tolyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, and 3,5-dimethylphenyl. ,5-dimethylphenyl group, 4-vinylphenyl group, o-isopropylphenyl group, m-isopropylphenyl group, p-isopropylphenyl group, 2,3-diisopropylphenyl group, 2,4-diisopropylphenyl group, 2,5-diisopropylphenyl group, 2,6-diisopropylphenyl group, 2,4,6-triisopropylphenyl group, 4-butylphenyl group, o-tert-butylphenyl group, m-tert-butylphenyl group, p-tert-butylphenyl group, 2,6-di(tert-butyl)phenyl group, 3,5- Alkylaryl groups such as di(tert-butyl)phenyl, 3,6-di(tert-butyl)phenyl, 4-tert-butyl-2,6-dimethylphenyl, 4-pentylphenyl, 4-octylphenyl, 4-(2,4,4-trimethyl-2-pentyl)phenyl, 2-dodecylphenyl, 3-dodecylphenyl, and 4-dodecylphenyl; 2,3-dihydro-4-indenyl, 1,2,3,5,6,7-hexahydro-4-s-indacenyl, and 8-methyl-1,2,3,5,6,7-hexahydro-4- Examples of such aryl groups include aryl groups having an alkanediyl group bonded thereto, such as an s-indacenyl group, a 5,6,7,8-tetrahydro-1-naphthyl group, a 5,6,7,8-tetrahydro-2-naphthyl group, a 3-methyl-5,6,7,8-tetrahydro-2-naphthyl group, and a 3,5,5,8,8-pentamethyl-5,6,7,8-tetrahydro-2-naphthyl group; aryl groups having one or more aryl groups bonded thereto, such as a biphenylyl group and a terphenylyl group; a cyclohexylmethylphenyl group, a benzylphenyl group, and a (dimethyl(phenyl)methyl)phenyl group.The hydrocarbon group may be, for example, a hydrocarbon group formed by combining a chain hydrocarbon group and an alicyclic hydrocarbon group, and examples thereof include a 1-methylcyclopropyl group, a 1-methylcyclohexyl group, a 2-methylcyclohexyl group, a 3-methylcyclohexyl group, a 4-methylcyclohexyl group, a 1,2-dimethylcyclohexyl group, a 1,3-dimethylcyclohexyl group, a 1,4-dimethylcyclohexyl group, a 2,3-dimethylcyclohexyl group, a 2,4-dimethylcyclohexyl group, a 2,5-dimethylcyclohexyl group, a 2,6-dimethylcyclohexyl group, a 3,4-dimethylcyclohexyl group, a 3,5-dimethylcyclohexyl group, a 2,2-dimethylcyclohexyl group, and a 3,3-dimethylcyclohexyl group. Examples of the alkyl groups include alicyclic hydrocarbon groups having one or more alkyl groups bonded thereto, such as an alkyl group, a 4,4-dimethylcyclohexyl group, a 2,4,6-trimethylcyclohexyl group, a 2,2,6,6-tetramethylcyclohexyl group, a 3,3,5,5-tetramethylcyclohexyl group, a 4-pentylcyclohexyl group, a 4-octylcyclohexyl group, and a 4-cyclohexylcyclohexyl group; and alkyl groups having one or more alicyclic hydrocarbon groups bonded thereto, such as a cyclopropylmethyl group, a cyclopropylethyl group, a cyclobutylmethyl group, a cyclobutylethyl group, a cyclopentylmethyl group, a cyclopentylethyl group, a cyclohexylmethyl group, a 2-methylcyclohexylmethyl group, a cyclohexylethyl group, and an adamantylmethyl group. The number of carbon atoms in the group formed by combining two or more of the chain hydrocarbon group, the alicyclic hydrocarbon group, and the aromatic hydrocarbon group is preferably 6 to 18, and more preferably 6 to 15.

[0017] Examples of the substituent that the hydrocarbon group having 1 to 20 carbon atoms may have include a halogen atom; a nitrile group; a nitro group; an amino group; a hydroxy group; an alkoxy group having 1 to 19 carbon atoms, such as a methoxy group or an ethoxy group; an aryloxy group having 6 to 19 carbon atoms, such as a phenyloxy group, a 1-naphthyloxy group or a 2-naphthyloxy group; a thiol group; an alkylthio group having 1 to 19 carbon atoms, such as a methylthio group or an ethylthio group; an allylthio group; an arylthio group having 6 to 19 carbon atoms, such as a phenylthio group, a 1-naphthylthio group or a 2-naphthylthio group; a sulfoxy group; an alkylsulfoxy group having 1 to 19 carbon atoms, such as a methylsulfoxy group or an ethylsulfoxy group; an arylsulfoxy group having 6 to 19 carbon atoms, such as a phenylsulfoxy group, a 1-naphthylsulfoxy group or a 2-naphthylsulfoxy group; a silyl group; a boryl group; a monomethylamino group, a dimethylamino group, a methyl ... alkylamino groups having 1 to 19 carbon atoms, such as an amino group, a trimethylamino group, a monoethylamino group, a diethylamino group, or a triethylamino group; arylamino groups having 6 to 19 carbon atoms, such as a monophenylamino group, a diphenylamino group, or a triphenylamino group; aralkylamino groups having 7 to 19 carbon atoms, such as a benzylamino group; a carboxy group; a carbamoyl group; alkylcarbonyl groups having 2 to 19 carbon atoms, such as an acetyl group or a propionyl group; arylcarbonyl groups having 7 to 19 carbon atoms, such as a benzoyl group, a 1-naphthylcarbonyl group, or a 2-naphthylcarbonyl group; alkoxycarbonyl groups having 2 to 19 carbon atoms, such as a methoxycarbonyl group or an ethoxycarbonyl group; and aryloxycarbonyl groups having 7 to 19 carbon atoms, such as a phenyloxycarbonyl group, a 1-naphthyloxycarbonyl group, or a 2-naphthyloxycarbonyl group. When the hydrocarbon group having 1 to 20 carbon atoms has a substituent, the total number of carbon atoms contained in the hydrocarbon group and the substituent is defined as the number of carbon atoms contained in the hydrocarbon group.

[0018] Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0019] The methylene group (-CH2-) contained in the hydrocarbon group is -O-, -CO- or -N(R B1 )- may be replaced.

[0020] R B1 represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms. B1 represents preferably a hydrogen atom or a hydrocarbon group having 1 to 15 carbon atoms, more preferably a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and even more preferably a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.

[0021] When a methylene group contained in the hydrocarbon group is replaced with -O- or -CO-, the number may be one or more. When a methylene group contained in the hydrocarbon group is replaced with -O- or -CO-, the total number of carbon atoms contained in the hydrocarbon group and the carbon atoms contained in the replaced group is defined as the number of carbon atoms of the hydrocarbon group. Specific examples of groups in which a methylene group contained in the hydrocarbon group is replaced with -O- or -CO- include groups represented by the following formulae (Y-1) to (Y-60). * represents a bond.

[0022] [ka]

[0023] [ka]

[0024] [ka]

[0025] The methylene group contained in the hydrocarbon group is -N(R B1 When a methylene group contained in the hydrocarbon group is replaced by -N(R )-, the number of the methylene groups may be one or more. B1 When a methylene group contained in the hydrocarbon group is replaced by -N(R )-, the total number of carbon atoms contained in the hydrocarbon group and the number of carbon atoms contained in the group that replaced it is the number of carbon atoms of the hydrocarbon group. B1Specific examples of the group substituted with )- include groups represented by the following formulae (Z-1) to (Z-48), in which * represents a bond.

[0026] [ka]

[0027] [ka]

[0028] R 9 and R 12 , and / or R 10 and R 11 may be bonded to each other to form a ring.

[0029] R 9 and R 12 , and / or R 10 and R 11 When they are bonded to each other to form a ring, R 9 and R 12 , and R 10 and R 11 The group to which R is bonded is a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent (the methylene group contained in the hydrocarbon group is -O-, -CO- or -N(R B1 )-, which may be replaced by a divalent group formed by removing one hydrogen atom. For example, R 9 and R 12 , and R 10 and R 11 The groups to which each is bonded are independently *-CO-O-CO-* or *-CO-N(R B1 )-CO-*, *-CO-O-CO-* or *-CO-N(R B1 )-CO-* and a divalent group containing the group. R 9 and R 12 , and / or R 10 and R 11 respectively form *-CO-O-CO-* or *-CO-N(R B1Examples of rings containing -CO-* (where * represents a bond) include R 9 and R 12 , R 10 and R 11 are each independently a divalent group represented by the following formulas (H-1) to (H-16): In formulas (H-1) to (H-16), * represents R 9 and R 12 , R 10 and R 11 represents the bond to the terrylene skeleton.

[0030] [ka]

[0031] [ka]

[0032] In a preferred embodiment, R in formula (Ia) and formula (Ib) 1 ~R 4 and R 9 ~R 12 R preferably represents a hydrogen atom. 1 ~R 4 and R 9 ~R 12 When represents a hydrogen atom, the heat resistance and solubility of the compound can be further improved.

[0033] In formula (Ia) and formula (Ib), R A1 each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a halogen atom, a hydroxy group, a carboxy group, -OR B2 , or -COOR B2 Represents.

[0034] R B2 represents a hydrocarbon group having 1 to 10 carbon atoms. Examples of the hydrocarbon group having 1 to 10 carbon atoms include those having up to 10 carbon atoms among the above-mentioned examples of the hydrocarbon group having 1 to 20 carbon atoms. R B2 represents a hydrocarbon group preferably having 1 to 8 carbon atoms. Therefore, -OR B2 Specific examples of the alkyl group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, a hexyloxy group, a heptyloxy group, an octyloxy group, a nonanyloxy group, a decyloxy group, a phenoxy group, a 1-methylpropoxy group, a sec-butoxy group, a tert-butoxy group, a (1-ethyl)pentyloxy group, and a (2-ethyl)hexyl group.

[0035] Also, -COOR B2 Specific examples of the alkyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, a (1-methyl)propoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, a butoxycarbonyl group, a pentyloxycarbonyl group, a (1-ethyl)pentyloxycarbonyl group, a hexyloxycarbonyl group, a (2-ethyl)hexyloxycarbonyl group, a heptyloxycarbonyl group, and an octyloxycarbonyl group.

[0036] In a preferred embodiment, R in formula (Ia) and formula (Ib) A1 From the viewpoint of improving the heat resistance and solubility of the compound, preferably represents a hydrocarbon group having 1 to 10 carbon atoms, more preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, isobutyl group, tert-butyl group, tert-amyl group or tert-octyl group, and even more preferably a branched alkyl group such as a tert-butyl group, tert-amyl group or tert-octyl group.

[0037] Each n independently represents an integer of 1 to 5. From the viewpoint of improving heat resistance and solubility, n is preferably 1 to 4, more preferably 1 to 3, and particularly preferably 1 or 2. When n is 1, R A1 is preferably bonded to the m- or p-position, more preferably to the p-position.

[0038] V, W, X, and Y each independently represent a carbon atom or a nitrogen atom;1 represents an aromatic heterocycle containing a nitrogen atom which may have a substituent, which is formed together with V and W, and ring Z 2 represents an aromatic heterocycle containing a nitrogen atom which may have a substituent, which is formed together with X and Y.

[0039] Ring Z 1 and Z 2 may be monocyclic or polycyclic. Ring Z 1 and Z 2 The number of carbon atoms in each of the groups is independently preferably 3 to 20, more preferably 3 to 18, and particularly preferably 3 to 12. The aromatic heterocycle is preferably a 5- to 12-membered ring, more preferably a 5- to 10-membered ring, and even more preferably a 5- to 9-membered ring.

[0040] Ring Z 1 and Z 2 The number of nitrogen atoms in the ring Z is preferably 1 to 3, more preferably 1 to 2, and even more preferably 2. Therefore, in a preferred embodiment, 1 and ring Z 2 Preferably, each independently represents an aromatic heterocycle containing two nitrogen atoms which may have a substituent.

[0041] Ring Z 1 and Z 2 Examples of aromatic heterocycles containing a nitrogen atom that form the following include: 5-membered unsaturated heterocycles such as pyrrole, 1-methylpyrrole, 2,5-dimethylpyrrole, etc., pyrazole, such as pyrazole, 1-methylpyrazole, 2-methylpyrazole, 3-methylpyrazole, 4-methylpyrazole, 5-methylpyrazole, etc., imidazole, such as imidazole, 1,2,3-triazole, and 1,2,4-triazole, etc.; 6-membered unsaturated heterocycles such as pyridine, pyridazine, pyrimidine, 6-methylpyrimidine, etc., pyrazine, and 1,3,5-triazine; fused bicyclic heterocycles such as indazole, indoline, isoindoline, indole, indolizine, benzimidazole, quinoline, isoquinoline, quinoxalines such as 5,6,7,8-tetrahydro(3-methyl)quinoxaline and 3-methylquinoxaline, quinazoline, cinnoline, phthalazine, naphthyridine, purine, pteridine, benzopyrazole, and benzopiperidine; condensed tricyclic heterocycles such as carbazole, acridine and phenazine; and the like.

[0042] Also, ring Z 1 and Z 2 may contain atoms other than nitrogen atoms as heteroatoms. Examples of such heteroatoms include oxygen atoms and sulfur atoms. Therefore, ring Z 1 and Z 2 may contain a nitrogen atom and an oxygen atom, a nitrogen atom and a sulfur atom, or a nitrogen atom, an oxygen atom and a sulfur atom.

[0043] Examples of heterocycles containing a nitrogen atom and an oxygen atom include monocyclic unsaturated heterocycles such as isothiazole, oxazole, oxazoles such as 4-methyloxazole, and isoxazoles such as 2-methylisoxazole, 3-methylisoxazole, 4-methylisoxazole, and 5-methylisoxazole; fused bicyclic heterocycles such as benzoxazole, benzisoxazole, benzoxazine, benzodioxane, and benzimidazoline; condensed tricyclic heterocycles such as phenoxazine; and the like.

[0044] Examples of heterocyclic rings containing a nitrogen atom and a sulfur atom include Examples include 5-membered unsaturated heterocycles such as thiazole; fused bicyclic heterocycles such as benzothiazole; and fused tricyclic heterocycles such as phenothiazine.

[0045] Ring Z 1 and Z 2may have a substituent, and examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, a cyano group, a nitro group, a hydroxy group, a substituted or unsubstituted amino group, and an alkoxy group having 1 to 8 carbon atoms.

[0046] Ring Z 1 and Z 2 In the formula (I), V, W, X, and Y may all be carbon atoms, but it is preferred that at least one of V and W, and at least one of X and Y is a nitrogen atom, from the viewpoint of heat resistance and solubility of the compound.

[0047] Among these, from the viewpoint of heat resistance and solubility, it is preferable that at least one compound selected from the group consisting of compounds represented by formula (Ia) and formula (Ib) is a compound represented by formula (I-1) to formula (I-22).

[0048] [Table 1]

[0049] In Table 1, (ZZ-1) to (ZZ-22) represent the following structures: * in each group represents a bond.

[0050] [ka]

[0051] [ka]

[0052] In formulas (ZZ-1) to (ZZ-22), R 13each independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, a halogen atom, a hydroxy group, or a carboxy group, and a methylene group contained in the hydrocarbon group may be replaced with -O- or -CO-. Examples of the hydrocarbon group having 1 to 10 carbon atoms include the same hydrocarbon groups as those described above. Each m independently represents an integer of 1 to 4. When a methylene group contained in the hydrocarbon group is replaced with -O- or -CO-, the total number of carbon atoms contained in the hydrocarbon group and the group replacing it is considered to be the number of carbon atoms of the hydrocarbon group.

[0053] R 13 From the viewpoint of improving heat resistance and solubility, each of the groups preferably independently represents a hydrogen atom, a hydrocarbon group having 1 to 10 carbon atoms which may have a substituent, a chlorine atom, or an alkoxy group having 1 to 10 carbon atoms, and more preferably a hydrocarbon group having 1 to 10 prime numbers or a chlorine atom.

[0054] Therefore, from the viewpoint of heat resistance and solubility, the compound of the present invention is preferably a compound represented by formula (I-5), (I-15), or (I-22), and more preferably a compound represented by formula (I-15) or (I-22).

[0055] The compound of the present invention is at least one selected from the group consisting of compounds represented by formula (Ia) and formula (Ib), and preferably includes both the compound represented by formula (Ia) and the compound represented by formula (Ib). When the compound of the present invention includes both the compound represented by formula (Ia) and the compound represented by formula (Ib), the heat resistance of the obtained optical filter can be improved.

[0056] The compound of the present invention has excellent solubility in solvents. For example, the solubility of the compound of the present invention in cyclic ketones (e.g., cyclopentanone, cyclohexanone) is preferably 0.5% or more, more preferably 0.8% or more, even more preferably 0.9% or more, even more preferably 1.0% or more, and particularly preferably 1.1% or more, or 1.2% or more. The excellent solubility of the compound of the present invention in solvents facilitates the preparation of a resin composition when producing an optical filter. Furthermore, an optical filter with excellent smoothness can be obtained. The upper limit of the solubility in cyclohexanone is not particularly limited, but is usually 10% or less, or 5% or less. The solubility can be determined, for example, based on the method described in the Examples below.

[0057] In a preferred embodiment of the present invention, at least one compound selected from the group consisting of compounds represented by formula (Ia) and formula (Ib) is dissolved in N,N-dimethylformamide (DMF), and the absorption maximum wavelength λ measured in the wavelength range of 300 to 1400 nm using an ultraviolet-visible spectrophotometer is max [nm] is preferably greater than 700 nm, more preferably 710 to 930 nm, even more preferably 715 to 900 nm, still more preferably 720 to 870 nm, and particularly preferably 725 to 870 nm. max When the absorption maximum wavelength λ is within the above range, the compound can be suitably used as a near-infrared absorbing dye. max can be determined, for example, based on the method described in the Examples below.

[0058] In a preferred embodiment of the present invention, the thermal decomposition temperature of at least one compound selected from the group consisting of compounds represented by formula (Ia) and formula (Ib) is preferably 300°C or higher, more preferably 325°C or higher, even more preferably 350°C or higher, even more preferably greater than 350°C, particularly preferably 360°C or higher, particularly preferably greater than 360°C, or 365°C or higher. When the thermal decomposition temperature of at least one compound selected from the group consisting of compounds represented by formula (Ia) and formula (Ib) is above the lower limit, the compound exhibits excellent heat resistance, making it possible to stably produce optical filters from the compound. The thermal decomposition temperature of the compound is not particularly limited, as the higher the temperature, the better the heat resistance, but is typically 500°C or lower, or 480°C or lower. The thermal decomposition temperature can be measured using a thermogravimetric differential thermal analyzer (TG-DTA) and can be determined, for example, according to the method described in the Examples below.

[0059] The compounds represented by formula (Ia) and formula (Ib) can be synthesized by condensation reaction of a compound having a terylene skeleton obtained by the method described in JP-A-2022-126586 with an amine compound in the presence of a zinc acetate catalyst.

[0060] <Resin composition> The present invention encompasses a resin composition comprising at least one compound selected from the group consisting of compounds represented by formula (Ia) and formula (Ib) and an alkali-soluble resin.

[0061] In the resin composition of the present invention, the content of at least one compound selected from the group consisting of compounds represented by formula (Ia) and formula (Ib) is preferably 1 to 30 parts by mass, more preferably 1.5 to 25 parts by mass, and even more preferably 1.8 to 20 parts by mass, in total, relative to 100 parts by mass of the solid content of the resin composition. When the content of at least one compound selected from the group consisting of compounds represented by formula (Ia) and formula (Ib) is within the above range, the heat resistance of the obtained optical filter can be improved.

[0062] (alkali-soluble resin) The resin composition of the present invention preferably contains an alkali-soluble resin, which is preferably an alkali-soluble resin having a carboxylic acid.

[0063] Examples of the alkali-soluble resin include the following resins [K1] to [K6]. Resin [K1]: a copolymer having structural units derived from at least one member (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and structural units derived from a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond; Resin [K2]: a copolymer having structural units derived from (a), structural units derived from (b), and structural units derived from a monomer (c) copolymerizable with (a) (however, different from (a) and (b)) (hereinafter, sometimes referred to as "(c)"); Resin [K3]: a copolymer having structural units derived from (a) and structural units derived from (c); Resin [K4]: a copolymer having a structural unit derived from (a) to which (b) has been added, and a structural unit derived from (c); Resin [K5]: a copolymer having a structural unit derived from (b) to which (a) has been added, and a structural unit derived from (c); Resin [K6]: A copolymer having a structural unit derived from (c) and a structural unit obtained by adding (a) to a structural unit derived from (b) and further adding a carboxylic acid anhydride.

[0064] Examples of the monomer (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid; Unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, and 1,4-cyclohexenedicarboxylic acid; Bicyclounsaturated compounds containing a carboxy group, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene; carboxylic acid anhydrides such as the anhydrides of the above unsaturated dicarboxylic acids except fumaric acid and mesaconic acid; Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids, such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate; Unsaturated acrylates containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)acrylic acid; and the like. Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferred from the viewpoint of copolymerization reactivity and solubility of the resulting resin in an alkaline aqueous solution. In this specification, "(meth)acrylic acid" refers to at least one selected from the group consisting of acrylic acid and methacrylic acid. The terms "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

[0065] Monomer (b) refers to a polymerizable compound having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring (oxolane ring)) and an ethylenically unsaturated bond. Monomer (b) is preferably a monomer having a cyclic ether having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0066] Examples of the monomer (b) include a monomer having an oxiranyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b1)"), a monomer having an oxetanyl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b2)"), and a monomer having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter, sometimes referred to as "monomer (b3)").

[0067] Examples of the monomer (b1) include a monomer having a structure in which an unsaturated aliphatic hydrocarbon is epoxidized (hereinafter, may be referred to as "monomer (b1-1)") and a monomer having a structure in which an unsaturated alicyclic hydrocarbon is epoxidized (hereinafter, may be referred to as "monomer (b1-2)").

[0068] As the monomer (b1-1), a monomer having a glycidyl group and an ethylenically unsaturated bond is preferred. Specific examples of the monomer (b1-1) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis( glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene, and the like.

[0069] Examples of the monomer (b1-2) include vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., CELLOXIDE (registered trademark) 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., CYCLOMER (registered trademark) A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., CYCLOMER (registered trademark) M100; manufactured by Daicel Corporation), compounds represented by formula (BI), and compounds represented by formula (BII).

[0070] [ka]

[0071] In formula (BI) and formula (BII), R a and R b are each independently a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group. X a and X b are, independently of each other, a single bond, *-R c -, *-R c -O-, *-R c -S- or *-R c represents -NH-. R c represents an alkanediyl group having 1 to 6 carbon atoms. * represents a bond to O.

[0072] Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.

[0073] Examples of alkyl groups in which a hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.

[0074] R a and R b Preferred examples of the alkyl group include a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, and a 2-hydroxyethyl group, and more preferred examples include a hydrogen atom and a methyl group.

[0075] Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group.

[0076] X a and X b Preferred examples of the alkyl group include a single bond, a methylene group, an ethylene group, a *-CH2-O- (* represents a bond to O) group, and a *-CH2CH2-O- group, and more preferred examples include a single bond and a *-CH2CH2-O- group (* represents a bond to O).

[0077] The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone, or the compound represented by formula (BI) and the compound represented by formula (BII) may be used in combination. When these are used in combination, the content ratio of the compound represented by formula (BI) and the compound represented by formula (BII) is preferably 5:95 to 95:5, more preferably 10:90 to 90:10, and even more preferably 20:80 to 80:20, on a molar basis.

[0078] The monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond is preferably a monomer having an oxetanyl group and a (meth)acryloyloxy group. Examples of the monomer (b2) include 3-methyl-3-(meth)acryloyloxymethyloxetane, 3-ethyl-3-(meth)acryloyloxymethyloxetane, 3-methyl-3-(meth)acryloyloxyethyloxetane, and 3-ethyl-3-(meth)acryloyloxyethyloxetane.

[0079] The monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond is preferably a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group. Examples of the monomer (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0080] Examples of the monomer (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0] 2,6 ]decan-8-yl(meth)acrylate (commonly known in the art as "dicyclopentanyl(meth)acrylate" and sometimes called "tricyclodecyl(meth)acrylate"), tricyclo[5.2.1.0 2,6 ] decan-9-yl (meth)acrylate, tricyclo[5.2.1.0 2,6 ]decen-8-yl(meth)acrylate (commonly known in the art as "dicyclopentenyl(meth)acrylate"), tricyclo[5.2.1.0 2,6](meth)acrylic acid esters such as decene-9-yl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate; hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene Bicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept bicyclounsaturated compounds such as 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene; dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide; Examples include vinyl group-containing aromatic compounds such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, and p-methoxystyrene; vinyl group-containing nitriles such as (meth)acrylonitrile; halogenated hydrocarbons such as vinyl chloride and vinylidene chloride; vinyl group-containing amides such as (meth)acrylamide; esters such as vinyl acetate; and dienes such as 1,3-butadiene, isoprene, and 2,3-dimethyl-1,3-butadiene. Among these, styrene, vinyltoluene, tricyclo[5.2.1.0] and cyclopentyl methyl ether are preferred from the viewpoint of copolymerization reactivity and heat resistance. 2,6 ]Decan-8-yl (meth)acrylate, tricyclo[5.2.1.0 2,6 ] decan-9-yl (meth)acrylate, tricyclo[5.2.1.0 2,6 ]decene-8-yl (meth)acrylate, tricyclo[5.2.1.0 2,6 ]decen-9-yl(meth)acrylate, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, and benzyl(meth)acrylate are preferred.

[0081] In the resin [K1], the ratio of the structural units derived from each of these is as follows: Structural units derived from (a): 2 to 60 mol% Structural units derived from (b): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol% Structural units derived from (b): 50 to 90 mol% It is more preferable that: When the ratio of the structural units in the resin [K1] is within the above range, the storage stability of the resin composition and the heat resistance of the resulting optical filter can be excellent.

[0082] Resin [K1] can be produced, for example, by the method described in the literature "Experimental Methods of Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published March 1, 1972) and by reference to the references described in said literature.

[0083] Specifically, a method can be exemplified in which predetermined amounts of (a) and (b), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and the atmosphere is deoxygenated, for example by replacing oxygen with nitrogen, followed by heating and keeping the temperature while stirring. The polymerization initiator, solvent, and the like used here are not particularly limited, and those commonly used in the relevant field can be used. For example, polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.). Solvents that dissolve the respective monomers can be used, and examples of the solvents for the resin composition of the present invention include the solvents described below.

[0084] The resulting copolymer may be used as a solution after the reaction as is, or may be a concentrated or diluted solution, or may be extracted as a solid (powder) by a method such as reprecipitation. In particular, by using a solvent contained in the resin composition of the present invention as a solvent during the polymerization, the solution after the reaction can be used as is for preparing the resin composition of the present invention, thereby simplifying the production process of the resin composition of the present invention.

[0085] In the resin [K2], the ratio of the structural units derived from each of these is as follows: Structural units derived from (a): 2 to 45 mol% Structural units derived from (b): 2 to 95 mol% Structural units derived from (c): 1 to 65 mol% Preferably, Structural units derived from (a): 5 to 40 mol% Structural units derived from (b): 5 to 80 mol% Structural units derived from (c): 5 to 60 mol% It is more preferable that: When the ratio of the structural units of the resin [K2] is within the above range, the storage stability of the resin composition can be improved, and the heat resistance and mechanical strength of the resulting optical filter can be improved.

[0086] Resin [K2] can be produced, for example, in the same manner as described above for producing resin [K1].

[0087] In the resin [K3], the ratio of the structural units derived from each of these is as follows: Structural units derived from (a): 2 to 60 mol% Structural units derived from (c): 40 to 98 mol% It is preferred that Structural units derived from (a): 10 to 50 mol% Structural units derived from (c): 50 to 90 mol% It is more preferable that: Resin [K3] can be produced, for example, in the same manner as described above for producing resin [K1].

[0088] Resin [K4] can be produced by obtaining a copolymer of (a) and (c), and then adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic acid anhydride contained in (a). First, a copolymer of (a) and (c) is produced in the same manner as described for the production of resin [K1]. In this case, the ratio of the structural units derived from each is preferably the same as that described for resin [K3].

[0089] Next, a part of the carboxylic acid and / or carboxylic acid anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms contained in (b). Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air from nitrogen, and (b), a reaction catalyst for the reaction of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether (e.g., tris(dimethylaminomethyl)phenol, etc.), a polymerization inhibitor (e.g., hydroquinone, etc.), etc. are placed in the flask, and the mixture is reacted, for example, at 60 to 130°C for 1 to 10 hours to produce the resin [K4]. The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, per 100 mol of (a). By using this range, the storage stability of the resin composition and the heat resistance of the resulting optical filter can be improved. Because the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) used in resin [K4], and (b1-1) is even more preferred. The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total of (a), (b), and (c).The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass per 100 parts by mass of the total of (a), (b), and (c). The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc. As with the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the amount of heat generated by the polymerization, etc.

[0090] Resin [K5] is obtained in the first step by the same method as in the production of resin [K1] described above, to obtain a copolymer of (b) and (c). As in the above, the obtained copolymer may be used as a solution after the reaction as is, a concentrated or diluted solution, or a solid (powder) obtained by a method such as reprecipitation. The ratios of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer are as follows: Structural units derived from (b): 5 to 95 mol% Structural units derived from (c): 5 to 95 mol% Preferably, Structural units derived from (b): 10 to 90 mol% Structural units derived from (c): 10 to 90 mol% It is more preferable that:

[0091] Furthermore, under the same conditions as in the production method of resin [K4], resin [K5] can be obtained by reacting the cyclic ether derived from (b) contained in the copolymer of (b) and (c) with the carboxylic acid or carboxylic anhydride contained in (a). The amount of (a) used to react with the copolymer is preferably 5 to 80 moles per 100 moles of (b). Because the reactivity of cyclic ethers is high and unreacted (b) is unlikely to remain, (b1) is preferred as (b) used in resin [K5], and (b1-1) is more preferred.

[0092] Resin [K6] is a resin obtained by further reacting resin [K5] with a carboxylic acid anhydride. The hydroxyl group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride is reacted with the carboxylic acid anhydride. Examples of the carboxylic acid anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc. The amount of the carboxylic acid anhydride used is preferably 0.5 to 1 mole per mole of the amount of (a) used.

[0093] Specific examples of alkali-soluble resins include 3,4-epoxycyclohexylmethyl (meth)acrylate / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ] Decyl acrylate / (meth)acrylic acid copolymer and other resins [K1]; glycidyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer, glycidyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6] Decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 2,6 ]decyl acrylate / (meth)acrylic acid / N-cyclohexylmaleimide / 2-hydroxyethyl (meth)acrylate copolymer, 3-methyl-3-(meth)acryloyloxymethyloxetane / (meth)acrylic acid / styrene copolymer, etc. [K2]; benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer, etc. [K3]; resins obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, tricyclodecyl Resins such as resins obtained by adding glycidyl (meth)acrylate to a (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer [K4]; resins obtained by reacting a tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymer with (meth)acrylic acid, resins such as resins obtained by reacting a tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate copolymer with (meth)acrylic acid [K5]; and resins such as resins obtained by reacting a tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate copolymer with (meth)acrylic acid and further reacting tetrahydrophthalic anhydride with the resin [K6].

[0094] From the viewpoint of heat resistance, the alkali-soluble resin is more preferably resin [K1] or resin [K2], and particularly preferably resin [K1].

[0095] The weight average molecular weight (Mw) of the alkali-soluble resin in terms of polystyrene is preferably 1,000 to 100,000, more preferably 2,000 to 50,000, and even more preferably 3,000 to 30,000. When the weight average molecular weight is within the above range, the heat resistance of the obtained optical filter can be improved. The dispersity of the alkali-soluble resin [weight average molecular weight (Mw) / number average molecular weight (Mn)] is preferably 1-6, more preferably 1.001-4, and even more preferably 1.01-4.

[0096] The acid value (solid content equivalent) of the alkali-soluble resin is preferably 10 mg-KOH / g to 300 mg-KOH / g, more preferably 20 mg-KOH / g to 250 mg-KOH / g, even more preferably 25 mg-KOH / g to 200 mg-KOH / g, still more preferably 30 mg-KOH / g to 150 mg-KOH / g, and particularly preferably 60 mg-KOH / g to 135 mg-KOH / g. The acid value is measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin, and can be determined, for example, by titration with an aqueous potassium hydroxide solution.

[0097] The content of the alkali-soluble resin is preferably 5 to 50 mass %, more preferably 10 to 40 mass %, and even more preferably 15 to 30 mass %, based on 100 mass % of the solid content of the resin composition. When the content of the alkali-soluble resin is within the above range, the heat resistance of the obtained optical filter can be improved.

[0098] The resin composition of the present invention preferably further contains a polymerizable compound and a polymerization initiator in addition to at least one compound selected from the group consisting of compounds represented by formula (Ia) and formula (Ib) and an alkali-soluble resin.

[0099] (polymerizable compound) The polymerizable compound is a compound that can be polymerized by active radicals and / or acids generated from a polymerization initiator, and examples thereof include compounds having a polymerizable ethylenically unsaturated bond, and are preferably (meth)acrylic acid ester compounds.

[0100] Examples of polymerizable compounds having one ethylenically unsaturated bond include nonylphenyl carbitol acrylate, 2-hydroxy-3-phenoxypropyl acrylate, 2-ethylhexyl carbitol acrylate, 2-hydroxyethyl acrylate, N-vinylpyrrolidone, and the above-mentioned monomers (a), (b), and (c).

[0101] Examples of polymerizable compounds having two ethylenically unsaturated bonds include 1,6-hexanediol di(meth)acrylate, ethylene glycol di(meth)acrylate, neopentyl glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, bis(acryloyloxyethyl) ether of bisphenol A, and 3-methylpentanediol di(meth)acrylate.

[0102] Among them, the polymerizable compound is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylenediaminetetraacetic acid ester ... Examples of the dipentaerythritol tetra(meth)acrylate include ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate, and preferably dipentaerythritol penta(meth)acrylate and dipentaerythritol hexa(meth)acrylate.

[0103] The weight average molecular weight of the polymerizable compound is preferably 50 to 4,000, more preferably 70 to 3,500, even more preferably 100 to 3,000, still more preferably 150 to 2,900, and particularly preferably 250 to 1,500.

[0104] The content of the polymerizable compound is, for example, 1 to 99 mass %, preferably 5 to 90 mass %, more preferably 10 to 80 mass %, and even more preferably 20 to 70 mass %, relative to the total amount of solids in the resin composition.

[0105] (Polymerization initiator) The polymerization initiator is not particularly limited as long as it is a compound that generates active radicals, acids, etc. by the action of light or heat and can initiate polymerization, and known polymerization initiators can be used.

[0106] Examples of the polymerization initiator include O-acyloxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine oxide compounds. Examples of these polymerization initiators include compounds described in JP-A-2022-126586.

[0107] The polymerization initiator is preferably a polymerization initiator containing at least one selected from the group consisting of an alkylphenone compound, a triazine compound, an acylphosphine oxide compound, an O-acyloxime compound, and a biimidazole compound, and more preferably a polymerization initiator containing an O-acyloxime compound.

[0108] The content of the polymerization initiator is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the alkali-soluble resin and polymerizable compound contained in the resin composition. When the content of the polymerization initiator is within this range, sensitivity tends to be increased and exposure time tends to be shortened, thereby improving productivity of the optical filter.

[0109] The resin composition of the present invention may contain components other than the alkali-soluble resin, the polymerizable compound, and the polymerization initiator.

[0110] (Polymerization initiator aid) The polymerization initiation aid is a compound or sensitizer used to promote the polymerization of a polymerizable compound whose polymerization has been initiated by a polymerization initiator. When a polymerization initiation aid is contained, it is usually used in combination with a polymerization initiator.

[0111] Examples of the polymerization initiation aid include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds. Examples of these polymerization initiation aids include compounds described in JP-A-2022-126586.

[0112] When these polymerization initiation aids are used, the content thereof is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, per 100 parts by mass of the total amount of the alkali-soluble resin and polymerizable compound contained in the resin composition.

[0113] (solvent) The solvent is not particularly limited, and any solvent commonly used in the relevant field can be used. Examples of the solvent include ester solvents (solvents containing -COO- in the molecule but not containing -O-), ether solvents (solvents containing -O- in the molecule but not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule but not containing -COO-), alcohol solvents (solvents containing OH in the molecule but not containing -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, etc. These solvents may be used alone or in combination of two or more. Examples of these solvents include the solvents described in JP 2022-126586 A.

[0114] As the solvent, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate and cyclohexanone are preferred.

[0115] When a solvent is contained, the content of the solvent is usually 99.99% by mass or less, preferably 40 to 99% by mass, more preferably 50 to 95% by mass, even more preferably 70 to 95% by mass, and even more preferably 75 to 90% by mass, based on the total amount of the resin composition. In other words, the total amount of solids in the resin composition is usually 0.01% by mass or more, preferably 1 to 60% by mass, more preferably 5 to 50% by mass, even more preferably 5 to 30% by mass, and even more preferably 10 to 25% by mass or less. When the solvent content is within the above range, good flatness is achieved during application.

[0116] (Leveling agent) Examples of leveling agents include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. These may have a polymerizable group in the side chain. Examples of these leveling agents include the leveling agents described in JP-A-2022-126586.

[0117] When a leveling agent is contained, the content of the leveling agent is preferably 0.0005 to 1 mass %, more preferably 0.001 to 0.5 mass %, and even more preferably 0.005 to 0.1 mass %, relative to the total amount of the resin composition. When the content of the leveling agent is within the above range, the flatness of the optical filter can be improved.

[0118] (Other ingredients) The resin composition may contain, as needed, additives known in the art, such as fillers, other polymer compounds, adhesion promoters, quenchers, antioxidants, light stabilizers, chain transfer agents, etc. The content of other components is not particularly limited as long as they do not adversely affect the performance of the resin composition and the optical filter obtained from the resin composition, but is usually about 0.0001 to 10% by mass, or 0.0005 to 8% by mass, based on the mass of the resin composition.

[0119] In the resin composition of the present invention, the maximum absorption wavelength λ in the wavelength range of 300 to 1400 nm max The maximum absorption wavelength λ of the resin composition is preferably greater than 700 nm. max When the maximum absorption wavelength λ is greater than 700 nm, the near-infrared light is sufficiently absorbed, making the film suitable for use as a near-infrared optical filter. max is more preferably 710 nm or more, even more preferably 715 nm or more, even more preferably 720 nm or more, and particularly preferably 725 nm or more. max is preferably 930 nm or less, more preferably 900 nm or less, and even more preferably 870 nm or less.

[0120] The maximum absorption wavelength in the wavelength range of 300 to 1400 nm can be measured using an ultraviolet-visible-near-infrared absorption spectrometer (e.g., V-770, manufactured by JASCO Corporation). The measurement method can be performed, for example, as follows. First, a measurement solution is prepared by diluting the resin composition with a solvent so that the content of a compound selected from the group consisting of compounds represented by formula (Ia) and formula (Ib) in the resin composition becomes 10 ppm by mass. The measurement solution thus prepared is placed in a 1 cm square quartz cell, and the spectrum is measured in the wavelength range of 300 to 1400 nm (data sampling interval: 1 nm) using an ultraviolet-visible-near-infrared absorption spectrometer. At this time, the wavelength showing the maximum value of absorbance is referred to as the maximum absorption wavelength λ max In this way, the maximum absorption wavelength can be determined. The maximum absorption wavelength tends not to fluctuate even when the alkali-soluble resin, polymerizable compound, polymerization initiator, etc. in the resin composition are present in the measurement solution. Therefore, for example, a solution containing the compound of the present invention and a solvent, from which the alkali-soluble resin, polymerizable compound, polymerization initiator, etc. have been removed from the resin composition, is prepared as a measurement solution, and the maximum absorption wavelength in the wavelength range of 300 to 1400 nm measured using this solution may be considered to be the maximum absorption wavelength in the wavelength range of 300 to 1400 nm of the resin composition.

[0121] <Method of manufacturing resin composition> The resin composition can be prepared by mixing the compound of the present invention, an alkali-soluble resin, a polymerizable compound (if used), a polymerization initiator, a solvent, a leveling agent, and other components, which are used as needed. Mixing can be carried out using known or conventional equipment and conditions.

[0122] After mixing the components, the resin composition is preferably filtered through a filter with a pore size of about 0.01 to 10 μm.

[0123] <Optical filter and its manufacturing method> The method for producing an optical filter from the resin composition of the present invention is not particularly limited, and known methods can be used. For example, a method can be used in which the resin composition of the present invention is applied to a substrate to form a coating film, and the coating film is cured. Therefore, the present invention includes a cured product of the resin composition of the present invention.

[0124] Examples of the substrate include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and silica-coated soda lime glass; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon substrates; and substrates in which a thin film of aluminum, silver, a silver / copper / palladium alloy, etc. is formed on the substrate. Other optical filters, resin films, transistors, circuits, etc. may be formed on the substrate.

[0125] The coating method may be a known method, such as a dropping method, a spin coating method, a slit coating method, a spray method, a roll coating method, a slit-and-spin coating method, a casting method, an inkjet method, flexographic printing, screen printing, gravure printing, or offset printing.

[0126] The thickness of the optical filter is not particularly limited and can be adjusted appropriately depending on the purpose and use, etc. The thickness of the optical filter may be, for example, 0.1 to 30 μm, preferably 0.1 to 20 μm, and more preferably 0.5 to 6 μm.

[0127] After the resin composition is applied to a substrate, it is usually dried by heating (pre-baking) and / or dried under reduced pressure to remove volatile components such as the solvent, thereby obtaining a cured product.

[0128] When drying by heating, the temperature is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When drying under reduced pressure is performed, it is preferably performed under a pressure of 50 to 150 Pa at a temperature of 20 to 25°C.

[0129] The process for producing an optical filter may include a process for forming a pattern. Examples of a method for forming a pattern include photolithography. When the optical filter is used as a flat optical filter, the process for forming a pattern does not need to be performed. The pattern is not particularly limited, and a pattern appropriate for the intended use is used.

[0130] For example, when a pattern is formed by photolithography, a film formed by applying the resin composition of the present invention to a substrate is dried (pre-baked) as necessary, and then exposed to light in a pattern through a mask (exposure step), and the unexposed portions are removed by alkaline development (development step), and the pattern is then heat-treated (post-bake step).

[0131] The light source used for exposure is preferably a light source that generates light with a wavelength of 250 to 450 nm. The light source used for exposure may be, for example, one that cuts out light of less than 350 nm using a filter that cuts out this wavelength range, or one that selectively extracts light of around 436 nm, around 408 nm, and around 365 nm using a bandpass filter that extracts these wavelength ranges. Specific examples of light sources used for exposure include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps.

[0132] For exposure, it is preferable to use an exposure device such as a mask aligner or stepper, since this allows for uniform irradiation of the entire exposure surface with parallel light rays and allows for accurate alignment of the photomask with the substrate on which the coating film is formed.

[0133] A pattern is formed on the cured product by bringing the exposed coating film (i.e., the cured product) into contact with a developer and developing it. The unexposed areas of the resin composition layer are dissolved in the developer and removed by development. Examples of the developer include aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide. The concentration of these alkaline compounds in the aqueous solution is preferably 0.01 to 10% by mass, more preferably 0.03 to 5% by mass. The developer may further contain a surfactant.

[0134] Examples of the developing method include a puddle method, a dipping method, a spray method, etc. During development, the substrate may be tilted at any angle. After development, it is preferable to wash the resulting pattern with water.

[0135] The resulting pattern is preferably post-baked. The post-baking temperature is preferably 150 to 250°C, more preferably 160 to 235°C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes. At least one compound selected from the group consisting of compounds represented by formula (Ia) and formula (Ib) of the present invention has a very high thermal decomposition onset temperature and is highly heat-resistant. Therefore, decomposition does not occur even when post-baked at high temperatures, such as those described above, and as a result, decomposition products are not contained in the resulting optical filter. When a compound with low heat resistance is used, the compound may partially decompose during the post-baking process, resulting in the inclusion of decomposition products. The inclusion of such decomposition products can sometimes impair the optical properties of the optical filter. However, when the compound of the present invention is used, such decomposition can be suppressed, thereby further improving the optical properties. For example, it is believed that the optical properties can be further improved by obtaining a sharp absorption peak and suppressing variations in optical properties within the optical filter.

[0136] The cured product of the present invention can be suitably used in optical filters. Preferred examples of optical filters include infrared cut filters and infrared transmission filters. Therefore, the present invention includes optical filters containing the cured product of the present invention.

[0137] <Solid-state imaging element> The present invention includes a solid-state imaging device including the optical filter of the present invention. The solid-state imaging device of the present invention can be used for various purposes, such as digital cameras, video cameras, electronic devices with imaging functions (smartphones, tablet terminals, etc.), vehicle-mounted cameras, surveillance cameras, and optical sensors. [Example]

[0138] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to the following examples, and can of course be practiced with appropriate modifications within the scope of the above and below-described aims, all of which are included within the technical scope of the present invention. In the following, unless otherwise specified, "parts" means "parts by mass" and "%" means "% by mass."

[0139] In the following examples, the structures of the compounds were confirmed by mass spectrometry (LC; Agilent 1200 model, MASS; Agilent LC / MSD6130 model, or MALDI-TOF MS; JEOL JMS-S3000).

[0140] The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin were measured by GPC under the following conditions. Apparatus: HLC-8120GPC (Tosoh Corporation) Column: TSK-GELG2000HXL Column temperature: 40℃ Solvent: tetrahydrofuran Flow rate: 1.0mL / min Solid concentration of the analytical sample: 0.001 to 0.01% by mass Injection volume: 50μL Detector: RI Calibration standard materials: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation) The ratio of the weight average molecular weight and the number average molecular weight (Mw / Mn) calculated in terms of polystyrene obtained above was taken as the dispersity.

[0141] <Synthesis Example 1> (Synthesis of Compound (II-1)) According to the description of Synthesis Example 10 of JP 2022-126586 A, a compound represented by formula (II-1) was obtained. [ka]

[0142] (Identification of Compound (II-1)) (Mass spectrometry) Ionization mode = ESI + : m / z= 777 Exact Mass: 776

[0143] <Synthesis Example 2> (Synthesis of Compound (II-2)) 20.0 parts of compound (II-1) obtained in Synthesis Example 1, 53 parts of bromine (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 1000 parts of chloroform (manufactured by Nacalai Tesque, Inc.) were mixed and stirred at 60°C for 16 hours. After cooling to 23°C, the mixture was added dropwise to a solution of 60 parts of sodium sulfite (manufactured by Kanto Chemical Co., Inc.) and 2000 parts of water, followed by separation. The resulting organic phase was dehydrated with anhydrous sodium sulfate (manufactured by Kanto Chemical Co., Inc.). The sodium sulfate was filtered, and the solvent was distilled off to obtain 19.5 parts of a yellow solid mixture of compounds represented by formulae (II-2) and (II-2a) (yield of compound (II-2) 58%, yield of compound (II-2a) 32%).

[0144] [ka]

[0145] (Identification of Compound (II-2)) (Mass spectrometry) Ionization mode = ESI+ : m / z= 1089 Exact Mass: 1088

[0146] (Identification of Compound (II-2a)) (Mass spectrometry) Ionization mode = ESI - : m / z= 957 Exact Mass: 958

[0147] <Synthesis Example 3> (Synthesis of Compound (II-3)) 1.0 part of a mixture consisting of compound (II-2) and compound (II-2a) obtained in Synthesis Example 2, 260 parts of chlorosulfonic acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 434 parts of dehydrated dichloromethane (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 23°C for 16 hours. After cooling to 23°C, the mixture was added dropwise to 1500 parts of water, resulting in the formation of a blue precipitate. The mixture containing this blue precipitate was filtered, and the residue after filtration was washed with 100 parts of water and 100 parts of acetone. The resulting residue was dried under reduced pressure at 60°C to obtain 11.3 parts of a compound represented by formula (II-3) (yield 100%). [ka]

[0148] (Identification of Compound (II-3)) (Mass spectrometry) Ionization mode = MALDI-TOF - : m / z= 827 Exact Mass: 828

[0149] <Synthesis Example 4> (Synthesis of Compound (II-4)) 20.0 parts of the compound (II-3) obtained in Synthesis Example 3, 35.8 parts of tert-butylphenol (Tokyo Chemical Industry Co., Ltd.), 102 parts of cesium carbonate (Kanto Chemical Co., Ltd.), and 1,000 parts of N-methylpyrrolidone (Kanto Chemical Co., Ltd.) were mixed and stirred at 120°C for 11 hours. After cooling to 23°C, 114 parts of concentrated hydrochloric acid (Fujifilm Wako Pure Chemical Industries, Ltd.) and 571 parts of water were added dropwise, resulting in the formation of a blue precipitate. The mixture containing this blue precipitate was filtered, and the residue was washed with 100 parts of water and 100 parts of acetone. The resulting residue was dried under reduced pressure at 60°C to obtain 16.0 parts of the compound represented by formula (II-4) (yield: 60%).

[0150] [ka]

[0151] (Identification of Compound (II-4)) (Mass spectrometry) Ionization mode = MALDI-TOF - : m / z= 1107 Exact Mass: 1108

[0152] Example 1 (Synthesis of Compounds (I-1a) and (I-1b)) 25.0 parts of compound (II-4) obtained in Synthesis Example 4, 12.5 parts of 1,8-diaminonaphthalene, 1.25 parts of zinc acetate (manufactured by Tokyo Chemical Industry Co., Ltd.), and 250 parts of quinoline (manufactured by Tokyo Chemical Industry Co., Ltd.) were mixed and stirred at 155° C. for 46 hours. After the solvent was distilled off, the mixture was purified by silica gel column chromatography (solvent: chloroform), yielding 8.75 parts of a mixture consisting of formula (I-1a) and formula (I-1b) (yield 35%).

[0153] [ka]

[0154] (Identification of Compounds (I-1a) and (I-1b)) (Mass spectrometry) Ionization mode = MALDI-TOF +: m / z= 1352 Exact Mass: 1353

[0155] <Example 2> (Synthesis of Compounds (I-2a) and (I-2b)) 9.72 parts of a mixture consisting of formula (I-2a) and formula (I-2b) were obtained (yield 31%) in the same manner as in Example 1, except that 12.5 parts of 1,8-diaminonaphthalene was replaced with 14.0 parts of 4,5-dichloro-1,2-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.).

[0156] [ka]

[0157] (Identification of Compounds (I-2a) and (I-2b)) (Mass spectrometry) Ionization mode = MALDI-TOF + : m / z= 1389 Exact Mass: 1388

[0158] Example 3 (Synthesis of Compounds (I-3a) and (I-3b)) A mixture of 8.38 parts of formula (I-3a) and formula (I-3b) was obtained in the same manner as in Example 1, except that 12.5 parts of 1,8-diaminonaphthalene was replaced with 10.9 parts of 4-methoxybenzene-1,2-diamine (Tokyo Chemical Industry Co., Ltd.) (yield: 28%).

[0159] [ka]

[0160] (Identification of Compounds (I-3a) and (I-3b)) (Mass spectrometry) Ionization mode = MALDI-TOF + : m / z= 1330 Exact Mass: 1329

[0161] <Synthesis Example 5> (Synthesis of Compound (V-2)) 32.0 parts of 3,4-dibromoaniline (manufactured by Aldrich) and 130 parts of acetic anhydride (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) were mixed and stirred at 110°C for 2 hours. After cooling to 23°C, the mixture was added dropwise to 500 parts of water. 500 parts of ethyl acetate and 65 parts of sodium hydroxide were added, and the mixture was separated. The resulting organic phase was dehydrated with anhydrous sodium sulfate (manufactured by Kanto Chemical Co., Inc.), and the sodium sulfate was filtered off, after which the solvent was distilled off. The resulting residue was purified by silica gel column chromatography (solvent: ethyl acetate / n-hexane = 1 / 10, weight ratio), yielding 27.0 parts of a pale yellow solid compound represented by formula (V-2) (yield 71%).

[0162] [ka]

[0163] (Identification of Compound (V-2)) (Mass spectrometry) Ionization mode = ESI + : m / z= 292 Exact Mass: 291

[0164] <Synthesis Example 6> (Synthesis of Compound (V-3)) 26.4 parts of the compound represented by formula (V-2) obtained in Synthesis Example 5 was mixed with 147 parts of concentrated sulfuric acid (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) and cooled to 0°C. 10 parts of nitric acid was added dropwise, and the mixture was stirred for 20 minutes. 2,000 parts of water was added dropwise, and the mixture was neutralized with aqueous ammonia until the pH reached 9.0, producing a yellow precipitate. The mixture containing this yellow precipitate was filtered, and the residue after filtration was washed with 100 parts of water. The resulting residue was purified by silica gel column chromatography (solvent: ethyl acetate / n-hexane = 2 / 100, weight ratio), yielding 21.0 parts of a compound represented by formula (V-3) as a yellow solid (yield 68%).

[0165] [ka]

[0166] (Identification of Compound (V-3)) (Mass spectrometry) Ionization mode = ESI + : m / z= 337 Exact Mass: 336

[0167] <Synthesis Example 7> (Synthesis of compound (V-4)) 20.0 parts of the compound (V-3) obtained in Synthesis Example 6, 57.2 parts of cyclohexylacetylene (manufactured by Combi-Blocks), 3.41 parts of tetrakis(triphenylphosphine)palladium(0) (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.64 parts of copper(I) iodide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), 300 parts of diisopropanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 178 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 80°C for 48 hours. After cooling to 23°C, 800 parts of ethyl acetate was added and the mixture was filtered through Celite. The solvent in the filtrate was distilled off, and the resulting residue was purified by silica gel column chromatography (solvent: ethyl acetate / n-hexane = 2 / 100, weight ratio), yielding 2.56 parts of a pale brown liquid compound represented by formula (V-4) (yield 11%).

[0168] [ka]

[0169] (Identification of Compound (V-4)) (Mass spectrometry) Ionization mode = ESI + : m / z= 393 Exact Mass: 392

[0170] <Synthesis Example 8> (Synthesis of compound (V-5)) 25.0 parts of the compound (V-4) obtained in Synthesis Example 7, 12.5 parts of ammonium bromide (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and 400 parts of 1,2-ethylenediamine (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 70°C for 8 hours. 500 parts of ethyl acetate and 500 parts of water were added, and the mixture was separated. The resulting organic phase was dehydrated with anhydrous sodium sulfate (manufactured by Kanto Chemical Co., Ltd.), and the sodium sulfate was filtered off, after which the solvent was distilled off. The resulting residue was purified by silica gel column chromatography (solvent: ethyl acetate / n-hexane = 1 / 10, weight ratio), yielding 20.1 parts of the compound represented by formula (V-5) as a pale yellow solid (yield 90%).

[0171] [ka]

[0172] (Identification of Compound (V-5)) (Mass spectrometry) Ionization mode = ESI + : m / z= 351 Exact Mass: 350

[0173] <Synthesis Example 9> (Synthesis of compound (V-6)) 13.0 parts of the compound (V-5) obtained in Synthesis Example 8, 2.6 parts of palladium / carbon (Pd 10%, 55% water-wet product, manufactured by Tokyo Chemical Industry Co., Ltd.), 400 parts of methanol (manufactured by Kanto Chemical Co., Ltd.), 2 kgf / cm 2 The mixture was stirred for 16 hours at 23° C. under a hydrogen atmosphere of 100° C. After filtration through Celite, the solvent in the filtrate was distilled off, and the resulting residue was purified by silica gel column chromatography (solvent: methanol / dichloromethane=1 / 100, weight ratio), yielding 11.0 parts of a pale brown liquid compound represented by formula (V-6) (yield 90%).

[0174] [ka]

[0175] (Identification of Compound (V-6)) (Mass spectrometry) Ionization mode = ESI + : m / z= 329 Exact Mass: 328

[0176] Example 4 (Synthesis of Compounds (I-4a) and (I-4b)) A mixture of 11.8 parts of formula (I-4a) and formula (I-4b) was obtained in the same manner as in Example 1, except that 12.5 parts of 1,8-diaminonaphthalene was replaced with 25.9 parts of the compound represented by formula (V-6) (yield 31%).

[0177] [ka]

[0178] (Identification of Compounds (I-4a) and (I-4b)) (Mass spectrometry) Ionization mode = MALDI-TOF + : m / z= 1694 Exact Mass: 1693

[0179] <Synthesis Example 10> (Synthesis of compound (V-8)) The same procedure as in Synthesis Example 5 was carried out except that 32.0 parts of 3,4-dibromoaniline was replaced with 25.9 parts of 4-bromo-2-nitroaniline, to obtain 29.5 parts of the compound represented by formula (V-8) (yield 68%).

[0180] [ka]

[0181] (Identification of Compound (V-8)) (Mass spectrometry) Ionization mode = ESI + : m / z= 259 Exact Mass: 258

[0182] <Synthesis Example 11> (Synthesis of compound (V-9)) 29.0 parts of the compound (V-8) obtained in Synthesis Example 10, 54.1 parts of 1-hexyne (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 3.41 parts of tetrakis(triphenylphosphine)palladium(0) (manufactured by Tokyo Chemical Industry Co., Ltd.), 5.33 parts of copper(I) iodide (manufactured by FUJIFILM Wako Pure Chemical Industries, Ltd.), 435 parts of diisopropanolamine (manufactured by Tokyo Chemical Industry Co., Ltd.), and 258 parts of tetrahydrofuran (manufactured by Kanto Chemical Co., Ltd.) were mixed and stirred at 80°C for 16 hours. After cooling to 23°C, 800 parts of ethyl acetate was added and the mixture was filtered through Celite. The solvent in the filtrate was distilled off, and the resulting residue was purified by silica gel column chromatography (solvent: ethyl acetate / n-hexane = 2 / 100, weight ratio), yielding 17.1 parts of the compound represented by formula (V-9) as a pale brown liquid (yield 59%).

[0183] [ka]

[0184] (Identification of Compound (V-9)) (Mass spectrometry) Ionization mode = ESI + : m / z= 261 Exact Mass: 260

[0185] <Synthesis Example 12> (Synthesis of compound (V-10)) 12.0 parts of a compound represented by formula (V-10) was obtained (yield 85%) in the same manner as in Synthesis Example 8, except that 25.0 parts of a compound represented by formula (V-4) was replaced with 16.6 parts of a compound represented by formula (V-9) obtained in Synthesis Example 11.

[0186] [ka]

[0187] (Identification of Compound (V-10)) (Mass spectrometry) Ionization mode = ESI + : m / z= 223 Exact Mass: 222

[0188] <Synthesis Example 13> (Synthesis of compound (V-11)) The same procedure as in Synthesis Example 9 was repeated, except that 13.0 parts of the compound represented by formula (V-5) was replaced with 8.2 parts of the compound represented by formula (V-10) obtained in Synthesis Example 12, to obtain 6.6 parts of the compound represented by formula (V-11) (yield 93%).

[0189] [ka]

[0190] (Identification of Compound (V-11)) (Mass spectrometry) Ionization mode = ESI + : m / z= 193 Exact Mass: 192

[0191] <Example 5> (Synthesis of Compounds (I-5a) and (I-5b)) A mixture of 8.75 parts of formula (I-5a) and formula (I-5b) was obtained in the same manner as in Example 1, except that 12.5 parts of 1,8-diaminonaphthalene was replaced with 15.1 parts of the compound represented by formula (V-11) (yield 27%).

[0192] [ka]

[0193] (Identification of Compounds (I-5a) and (I-5b)) (Mass spectrometry) Ionization mode = MALDI-TOF + : m / z= 1438 Exact Mass: 1437

[0194] <Comparative Example 1> (Synthesis of Compound (II-r)) The compound of formula (II-r) was obtained according to the specification of German Patent Application Publication No. 102012019495. [ka]

[0195] (Identification of Compound (II-r)) (Mass spectrometry) Ionization mode = MALDI-TOF + : m / z= 515 Exact Mass: 516

[0196] (Synthesis of Compounds (I-ra) and (I-rb)) The same procedure as in Example 1 was repeated, except that 25.0 parts of the compound represented by formula (II-4) was replaced with 11.6 parts of the compound represented by formula (II-r), and 12.5 parts of 1,8-diaminonaphthalene was replaced with 8.53 parts of 1,2-phenylenediamine (manufactured by Tokyo Chemical Industry Co., Ltd.), to obtain 11.6 parts of a mixture consisting of formula (I-ra) and formula (I-rb) (yield 78%).

[0197] [ka]

[0198] (Identification of Compounds (I-ra) and (I-rb)) (Mass spectrometry) Ionization mode = MALDI-TOF + : m / z= 661 Exact Mass: 660

[0199] <Solubility of Compounds> The solubility was measured by weighing approximately 50 mg of the compound (solute) obtained in each of the Examples and Comparative Examples into a 20 mL screw tube, adding approximately 450 mg of cyclohexanone (solvent), and then weighing the total amount of solute and solvent. The mixture was then stirred in a mixing rotor for 30 minutes. If dissolution was confirmed visually, the solubility was calculated using the following formula (h) based on the ratio of the solute mass to the total mass of the solute and solvent. If dissolution was not confirmed visually, 100 to 500 mg of solvent was added in increments until dissolution occurred, stirring was continued for 30 minutes in a mixing rotor after each addition. When dissolution was confirmed visually, the solubility was calculated using the ratio of the solute mass to the total mass of the solute and solvent based on the following formula (h). The results are shown in Table 2. Solubility (%) = (mass of solute) / (total mass of solute and solvent) × 100 (h)

[0200] [Table 2]

[0201] The compounds obtained in Examples 1 to 5 had high solubility in cyclohexanone and good solubility. Because the compounds of the present invention have high solubility in cyclohexanone, it is possible to produce a uniform resin composition when producing an optical filter, and as a result, it is thought that the uniformity of the optical properties of the obtained optical filter, etc. can also be improved.

[0202] <Absorption spectrum of compound> In a measuring flask, 0.10 g of each compound obtained in the Examples and Comparative Examples was dissolved in N,N-dimethylformamide to a volume of 0.02 L, and 0.002 L of this solution was diluted with chloroform to a volume of 0.2 L (concentration: 0.01 g / L). The absorption spectrum was measured in the wavelength range of 1400-300 nm using a UV-visible spectrophotometer (V-700; manufactured by JASCO Corporation) (quartz cell, optical path length: 1 cm). The wavelength at which the absorbance of this compound was greatest was designated as the maximum absorption wavelength λ. max The results are shown in Table 3.

[0203] [Table 3]

[0204] λ max The compounds obtained in Examples 1 to 5 are suitable as near-infrared absorbing dyes when λ is greater than 700 nm. max On the other hand, the compound obtained in Comparative Example 1 was not dissolved in N,N-dimethylformamide, and the absorption spectrum could not be measured.

[0205] <Heat resistance> The compounds obtained in the examples and comparative examples were measured for the thermal decomposition onset temperature at which a 5% weight loss occurred using a TG-DTA (thermogravimetric differential thermal analyzer) (TG-DTA8122, manufactured by Rigaku) ​​under a nitrogen atmosphere. The results are shown in Table 4.

[0206] [Table 4]

[0207] All of the compounds obtained in the examples have a thermal decomposition starting temperature of 300° C. or higher, are highly heat resistant, and can be suitably used as optical filters.

[0208] <Preparation of Resin Composition and Optical Filter> (Synthesis Example 14) A flask equipped with a reflux condenser, a dropping funnel, and a stirrer was filled with nitrogen to replace the atmosphere, and 280 parts of propylene glycol monomethyl ether acetate was added, followed by heating to 80°C with stirring. Next, 38 parts of acrylic acid, 3,4-epoxytricyclo[5.2.1.0] 2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 2,6 A mixed solution of 289 parts of a mixture of decan-9-yl acrylate (content ratio 1:1 by molar ratio) and 125 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. Meanwhile, a solution of 33 parts of 2,2-azobis(2,4-dimethylvaleronitrile) dissolved in 235 parts of propylene glycol monomethyl ether acetate was added dropwise over 6 hours. After the dropwise addition was completed, the mixture was kept at 80°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin B1) solution with a solids content of 35.1% and a viscosity of 125 mPa·s measured with a Brookfield viscometer (23°C). The weight-average molecular weight Mw of the resulting copolymer was 9.2×10 3 The resin B1 had a polydispersity of 2.08 and an acid value calculated as solid content of 77 mg-KOH / g.

[0209] [ka]

[0210] (Preparation of Resin Composition 1) The components were mixed in the following proportions to obtain a resin composition 1. TIFF2025129758000038.tif23164

[0211] (Preparation of Resin Composition 1') Next, the components were mixed in the following proportions to obtain a resin composition 1'. TIFF2025129758000039.tif43164

[0212] (Production of cured product (optical filter)) Resin composition 1' was applied by spin coating onto a 5 cm square glass substrate (Eagle XG; manufactured by Corning Incorporated) so that the film thickness after post-baking would be 2 μm, and then pre-baked at 100°C for 3 minutes to form a resin composition layer. After cooling, the resin composition layer formed on the substrate was exposed to 80 mJ / cm 2 in air using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). 2 After the light irradiation, the coating was post-baked in an oven at 230° C. for 30 minutes to obtain a cured product.

Claims

1. At least one compound selected from the group consisting of compounds represented by formula (Ia) and formula (Ib): 【Chemical 1】 [In formula (Ia) and formula (Ib), R １ ~R ４ and R ９ ~R １２ are each independently a hydrogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a halogen atom, a hydroxy group or a carboxy group, and a methylene group contained in the hydrocarbon group is -O-, -CO- or -N(R Ｂ１ ) - may be replaced by, R ９ and R １２ , and / or R １０ and R １１ may be bonded to each other to form a ring, R Ａ１ each independently represents a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, a halogen atom, a hydroxy group, a carboxy group, -OR Ｂ２ , or -COOR Ｂ２ represents n's each independently represent an integer of 1 to 5, R Ｂ１ represents a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, R Ｂ２ represents a hydrocarbon group having 1 to 10 carbon atoms, V, W, X, and Y each independently represent a carbon atom or a nitrogen atom; １ represents an aromatic heterocycle containing a nitrogen atom which may have a substituent, which is formed together with V and W; ring Z ２ represents an aromatic heterocycle containing a nitrogen atom which may have a substituent, which is formed together with X and Y.]

2. The ring Z １ and Ring Z ２ and each independently represent an aromatic heterocycle containing two nitrogen atoms which may have a substituent.

3. R in the formula (Ia) and formula (Ib) １ ~R ４ and R ９ ~R １２ 3. The compound according to claim 1, wherein represents a hydrogen atom.

4. R in the formula (Ia) and formula (Ib) Ａ１ The compound according to claim 1 or 2, wherein represents a hydrocarbon group having 1 to 10 carbon atoms.

5. A resin composition comprising at least one compound selected from the group consisting of compounds represented by formula (Ia) and formula (Ib) according to claim 1 or 2, and an alkali-soluble resin.

6. The resin composition according to claim 5 , further comprising a polymerizable compound and a polymerization initiator.

7. A cured product of the resin composition according to claim 6.

8. An optical filter comprising the cured product according to claim 7.

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

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