Cyanine compound, nitrogen-containing heterocyclic compound, and method for producing nitrogen-containing heterocyclic compound

Abstract

The present disclosure relates to a cyanine compound represented by formula (1). In formula (1), ring A1 and ring A2 each represents an optionally substituted aromatic hydrocarbon ring, an optionally substituted aromatic heterocyclic ring, or an optionally substituted fused ring containing these ring structures, ring B1 and ring B2 each represents a hydrocarbon ring optionally having a substituent and / or a fused ring structure, or a heterocyclic ring optionally having a substituent and / or a fused ring structure, and ring B1 and ring B2 each represents a hydrocarbon ring optionally having a substituent and / or a fused ring structure. (In the formula, R1 and R2 each represent an organic group, L represents a methine chain, and X-represents a monovalent anion in which the pKa of the conjugated acid is-8.0 or less. # imgabs0 #

Description

Technical Field

[0001] The present invention relates to a cyanine compound, a resin composition and an ink composition containing the cyanine compound, and a filter formed from the resin composition. The present invention also relates to a nitrogen-containing heterocyclic compound that can be used as a raw material or intermediate of the cyanine compound of the present invention and a method for producing the same. Background Art

[0002] Cyanine compounds are pigments having an absorption region in the near-infrared region, and various cyanine compounds are known so far (for example, Patent Documents 1 and 2).

[0003] Prior Art Documents

[0004] Patent Documents

[0005] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2021-134350

[0006] Patent Document 2: International Publication No. 2021 / 085372 Summary of the Invention

[0007] Problems to be Solved by the Invention

[0008] Cyanine compounds have an absorption region in the near-infrared region, and by utilizing the property of high transparency in the visible light region, their use in near-infrared cut-off filters, near-infrared absorbing films, etc. is expected. For example, sometimes blue glass is provided as one of the layer structures in a near-infrared cut-off filter, whereby transmission of near-infrared light in the wavelength region of 650 nm to 1100 nm can be suppressed. However, blue glass is liable to break, and thus there is a limit in terms of thinning. Cyanine compounds can absorb light in a wavelength region longer than the boundary between the visible light region and the near-infrared region, for example, a wavelength region longer than 650 nm. Therefore, if a cyanine compound is used, it can perform the function of replacing blue glass.

[0009] When applying a cyanine compound to the above-mentioned uses, it is desirable to dissolve the cyanine compound in an organic solvent, a resin, etc. to perform operations, whereby the handleability of the cyanine compound can be improved and the processability can be enhanced. However, cyanine compounds generally have low solubility in organic solvents and resins. For example, in the case of forming a filter from a resin composition containing a cyanine compound, in order to exhibit the spectral characteristics derived from the cyanine compound, the thickness of the filter needs to be formed to a certain extent. On the other hand, electronic devices such as filters require miniaturization and thinning. Therefore, in order to form a thinner filter, it is necessary to make the cyanine compound present in the filter at a higher concentration. In addition, in consideration of the function of replacing blue glass, it is desirable that the cyanine compound can absorb light in a longer-wavelength near-infrared region.

[0010] The present invention has been completed in view of the above circumstances, and an object thereof is to provide a cyanine compound having absorption on a longer wavelength side and excellent solubility in an organic solvent. The present invention also provides a resin composition and an ink composition containing the cyanine compound of the present invention, a filter formed from the resin composition, a nitrogen-containing heterocyclic compound that can be used as a raw material or an intermediate of the cyanine compound of the present invention, and a method for producing the same.

[0011] Solution to the problem

[0012] The cyanine compound, resin composition, ink composition, and filter of the present invention that can solve the above technical problems are as follows.

[0013] [1] A cyanine compound, characterized in that it is represented by the following formula (1).

[0014] [Chemical formula 1]

[0015]

[0016] [In formula (1), ring A 1 and ring A 2 each independently represent an optionally substituted aromatic hydrocarbon ring, an optionally substituted aromatic heterocyclic ring, or a condensed ring containing these ring structures and optionally having a substituent, ring B 1 and ring B 2 each independently represent a hydrocarbon ring optionally having a substituent and / or a condensed ring structure, or a heterocyclic ring optionally having a substituent and / or a condensed ring structure, and are spiro-bonded to an adjacent pyrrole ring, R 1 and R 2 each independently represent an organic group, L represents a methylene chain having 5 or more and 9 or less carbon atoms, and the methylene groups contained in the methylene chain each independently optionally have a substituent, and the substituents optionally link to each other, X - represents a monovalent anion having a pKa of the conjugate acid of -8.0 or less].

[0017] [2] The cyanine compound according to [1], wherein the ring B 1 and ring B 2 are a hydrocarbon ring having a condensed ring structure or a heterocyclic ring having a condensed ring structure.

[0018] [3] The cyanine compound according to [1] or [2], wherein the hydrocarbon ring or heterocyclic ring of the ring B 1 and ring B 2 that is spiro-bonded to an adjacent pyrrole ring has 5 or 6 ring members.

[0019] [4] The cyanine compound according to any one of [1] to [3], wherein the ring B 1 and ring B2 a hydrocarbon ring or a heterocyclic ring represented by the following formula (2-1) to formula (2-4).

[0020] [Chemical Formula 2]

[0021]

[0022] [In formula (2-1) to formula (2-4), ring C 1 to ring C 6 each independently represents a hydrocarbon ring optionally having a substituent, Y 1 represents -CH2-, -NH-, -O- or -S-, and Y 2 to Y 6 each independently represents -CH2-, -CH=, -NH-, -N=, -O- or -S-, and * represents a site of spiro bonding to an adjacent pyrrole ring].

[0023] [5] A resin composition, characterized by comprising a cyanine compound as described in any one of [1] to [4] and a resin component.

[0024] [6] The resin composition according to [5], wherein the resin composition further comprises a solvent.

[0025] [7] An ink composition, characterized by comprising a cyanine compound as described in any one of [1] to [4] and a solvent.

[0026] [8] A filter, characterized by having a resin layer formed of the resin composition as described in [4] or [5].

[0027] The method for producing a nitrogen-containing heterocyclic compound and the nitrogen-containing heterocyclic compound of the present invention are as follows.

[0028] [9] A method for producing a nitrogen-containing heterocyclic compound, characterized by comprising a step of reacting a compound represented by the following formula (5) with an alkylating agent represented by the following formula (6) to obtain a compound represented by the following formula (4).

[0029] [Chemical Formula 3]

[0030]

[0031] [In formula (4) to formula (6), ring A 1 represents an aromatic hydrocarbon ring optionally having a substituent, an aromatic heterocyclic ring optionally having a substituent, or a condensed ring containing these ring structures optionally having a substituent, ring B 1 represents a hydrocarbon ring optionally having a substituent and / or a condensed ring structure, or a heterocyclic ring optionally having a substituent and / or a condensed ring structure, which is spiro-bonded to an adjacent pyrrole ring, R 1represents an alkyl group, and Z represents an atom or group that provides a monovalent anion].

[0032]

[10] The method for producing a nitrogen-containing heterocyclic compound according to [9], wherein the R 1 is methyl, the alkylating agent is a halogenated methane or methyl sulfonate, and the Z - is a halide ion or a sulfonate ion.

[0033]

[11] A nitrogen-containing heterocyclic compound, characterized in that it is represented by the following formula (4).

[0034] [Chemical formula 4]

[0035]

[0036] [In formula (4), ring A 1 represents an optionally substituted aromatic hydrocarbon ring, an optionally substituted aromatic heterocyclic ring, or a fused ring containing these ring structures and optionally having substituents, and ring B 1 represents a hydrocarbon ring optionally having substituents and / or a fused ring structure, or a heterocyclic ring optionally having substituents and / or a fused ring structure, and is spiro-bonded to the adjacent pyrrole ring, R 1 represents an organic group, and Z - represents a halide ion or a sulfonate ion].

[0037] Advantages of the invention

[0038] The cyanine compound of the present invention has absorption on the longer wavelength side and excellent solubility in organic solvents. Description of the drawings

[0039] Figure 1 represents the absorption spectrum of the resin laminate substrate 1 produced in the examples.

[0040] Figure 2 represents the absorption spectrum of the comparative resin laminate substrate 1 produced in the examples. Detailed description of the invention

[0041] The cyanine compound of the present invention is represented by the following formula (1). In the following formula (1), ring A 1 and ring A 2 each independently represent an optionally substituted aromatic hydrocarbon ring, an optionally substituted aromatic heterocyclic ring, or a fused ring containing these ring structures and optionally having substituents, and ring B 1 and ring B 2 each independently represent a hydrocarbon ring optionally having substituents and / or a fused ring structure, or a heterocyclic ring optionally having substituents and / or a fused ring structure, and are spiro-bonded to the adjacent pyrrole ring, R 1 and R 2Each independently represents an organic group, L represents a methylene chain having 5 or more and 9 or less carbon atoms, each methylene contained in the methylene chain is independently optionally substituted, and the substituents are optionally linked to each other, X - represents a monovalent anion having a pKa of the conjugate acid of -8.0 or less. It should be noted that in cyanine compounds, there are sometimes compounds having a resonance relationship, and the cyanine compound of formula (1) also includes compounds having a resonance relationship.

[0042] [Chemical formula 5]

[0043]

[0044] The cyanine compound of the present invention has a structure represented by formula (1), so it has absorption on the longer wavelength side and excellent solubility in organic solvents. Therefore, the cyanine compound can be contained in the resin composition at a high concentration. In the case of forming a filter from the resin composition, even if the thickness is made thin, it can preferably absorb light in the near-infrared region on the longer wavelength side due to the cyanine compound. In addition, it also has excellent heat resistance. Therefore, when the cyanine compound is incorporated into the resin for heat molding or heat curing, etc., it is easy to suppress the decomposition of the cyanine compound. Therefore, even in the resin cured product, light in the visible light region can be transmitted with a high transmittance according to the absorption spectrum of the cyanine compound itself, and light in the near-infrared region is selectively absorbed. In the case of using the cyanine compound for ink liquid, etc., the cyanine compound can be contained in the ink liquid at a high concentration, and the color development property of the ink liquid can be improved.

[0045] In formula (1), ring A 1 and ring A 2 represent an aromatic hydrocarbon ring, an aromatic heterocyclic ring, or a condensed ring containing these ring structures, and these ring structures are optionally substituted. The cyanine compound has ring A 1 and ring A 2 , so the π-electron system is widely extended from the methylene chain L via the pyrrole ring to ring A 1 and ring A 2 , and the absorption wavelength can be made longer.

[0046] As the aromatic hydrocarbon ring of ring A 1 and ring A 2 , there is no particular limitation as long as it is a ring structure composed of carbon atoms and hydrogen atoms and has aromaticity. For example, a benzene ring, a naphthalene ring, a phenanthrene ring, an anthracene ring, a fluoranthene ring, etc. can be mentioned. The aromatic hydrocarbon ring can have only one ring structure or can be formed by condensation of two or more ring structures. Ring A 1 and ring A 2The aromatic heterocycle is not particularly limited as long as it contains one or more atoms selected from N (nitrogen atom), O (oxygen atom), and S (sulfur atom) in the ring structure and has aromaticity. Examples include: furan ring, thiophene ring, pyrrole ring, pyrazole ring, oxazole ring, thiazole ring, imidazole ring, pyridine ring, pyridazine ring, pyrimidine ring, pyrazine ring, purine ring, pteridine ring, etc. The aromatic heterocycle may have only one ring structure or may be formed by condensation of two or more ring structures. The fused ring containing these ring structures has a structure formed by condensation of an aromatic hydrocarbon ring and an aromatic heterocycle. Examples include: indole ring, isoindole ring, benzimidazole ring, quinoline ring, benzopyran ring, acridine ring, xanthene ring, carbazole ring, etc.

[0047] Ring A 1 and Ring A 2 optionally has a substituent (hereinafter referred to as "substituent P"). Examples of the substituent P include organic groups and polar functional groups. Examples of the organic group as the substituent P include: alkyl, alkoxy, alkylthio, alkoxycarbonyl, alkylsulfonyl, alkylsulfinyl, aryl, aralkyl, aryloxy, arylthio, aryloxycarbonyl, arylsulfonyl, arylsulfinyl, heteroaryl, amino, amido, sulfonamido, carboxyl (carboxylic acid group), cyano, etc. Examples of the polar functional group as the substituent P include: halogenated group, hydroxyl, nitro, sulfo (sulfonic acid group), etc.

[0048] Examples of the alkyl as the substituent P include: linear or branched alkyls such as methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl, etc.; cyclic (alicyclic) alkyls such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, etc. The alkyl optionally has a substituent. Examples of the substituent of the alkyl include: aryl, heteroaryl, halogenated group, hydroxyl, carboxyl, alkoxy, cyano, nitro, amino, sulfo, etc. Examples of the alkyl having a halogenated group include: monohalogenated alkyl, dihalogenated alkyl, alkyl having a trihalomethyl unit, perhalogenated alkyl, etc. As the halogenated group, a fluorine group, a chlorine group, and a bromine group are preferred, and a fluorine group is particularly preferred. The number of carbon atoms of the alkyl (excluding the carbon atoms of the substituent) is preferably 1 to 20. Specifically, if it is a linear or branched alkyl, the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, further preferably 1 to 5. If it is a cyclic alkyl, the number of carbon atoms is preferably 4 to 10, more preferably 5 to 8.

[0049] For specific examples of the alkyl contained in the alkoxy, alkylthio, alkoxycarbonyl, alkylsulfonyl, and alkylsulfinyl of the substituent P, refer to the above description of the alkyl.

[0050] Examples of the aryl group as the substituent P include phenyl, biphenyl, naphthyl, anthryl, phenanthryl, pyrenyl, indenyl, etc. The aryl group optionally has a substituent. Examples of the substituent of the aryl group include alkyl, alkoxy, heteroaryl, halogenated group, haloalkyl, hydroxy, cyano, nitro, amino, thiocyanate group, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfo, alkanesulfinyl, arenesulfinyl, alkanesulfonyl, arenesulfonyl, aminosulfonyl, etc. The number of carbon atoms of the aryl group (excluding the carbon atoms of the substituent) is preferably 6 to 20, more preferably 6 to 12.

[0051] Examples of the aralkyl group as the substituent P include benzyl, phenethyl, phenylpropyl, phenylbutyl, phenylpentyl, naphthylmethyl, etc. The aralkyl group optionally has a substituent. Examples of the substituent of the aralkyl group include alkyl, alkoxy, halogenated group, haloalkyl, cyano, nitro, thiocyanate group, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfo, alkanesulfinyl, arenesulfinyl, alkanesulfonyl, arenesulfonyl, aminosulfonyl, etc. The number of carbon atoms of the aralkyl group (excluding the carbon atoms of the substituent) is preferably 7 to 25, more preferably 7 to 15.

[0052] Specific examples of the aryl group contained in the aryloxy, arylthio, aryloxycarbonyl, arylsulfonyl, and arenesulfinyl of the substituent P can be referred to the above description of the aryl group.

[0053] Examples of the heteroaryl group as the substituent P include thienyl, thiopyranyl, isothiobenzopyranyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, pyrrolidinyl, pyrimidinyl, pyridazinyl, thiazolyl, isothiazolyl, furyl, pyranyl, etc. The heteroaryl group optionally has a substituent. Examples of the substituent of the heteroaryl group include alkyl, alkoxy, aryl, halogenated group, haloalkyl, hydroxy, cyano, amino, nitro, thiocyanate group, acyl, alkoxycarbonyl, aryloxycarbonyl, carbamoyl, sulfo, alkanesulfinyl, arenesulfinyl, alkanesulfonyl, arenesulfonyl, aminosulfonyl, etc. The number of carbon atoms of the heteroaryl group (excluding the carbon atoms of the substituent) is preferably 2 to 20, more preferably 3 to 15.

[0054] Examples of the amino group as the substituent P include the amino group represented by the formula: -NR a1 R a2 wherein, R a1 and R a2Each independently is a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, an aryl group, an aralkyl group, a heteroaryl group, etc. Specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group can be referred to the descriptions of these groups above. As the alkenyl group and alkynyl group, groups in which a part of the carbon-carbon single bonds of the alkyl groups exemplified above are replaced by double bonds or triple bonds can be mentioned. R a1 and R a2 optionally link to each other to form a ring.

[0055] As the amide group of the substituent P, an amide group represented by the formula: -NH-C(=O)-R a3 can be mentioned, wherein R a3 is an alkyl group, an aryl group, an aralkyl group, a heteroaryl group, etc. Specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group can be referred to the descriptions of these groups above.

[0056] As the sulfonamide group of the substituent P, a sulfonamide group represented by the formula: -NH-SO2-R a4 can be mentioned, wherein R a4 is an alkyl group, an aryl group, an aralkyl group, a heteroaryl group, etc. Specific examples of the alkyl group, aryl group, aralkyl group, and heteroaryl group can be referred to the descriptions of these groups above.

[0057] As the halogenated group of the substituent P, fluorine group, chlorine group, bromine group, iodine group, etc. can be mentioned.

[0058] As the substituent P, among the above, an alkyl group, an alkoxy group, an alkylthio group, an alkoxycarbonyl group, an aryl group, an aryloxycarbonyl group, a cyano group, a halogenated group, a nitro group are preferred, and an alkyl group, an alkoxy group, an alkylthio group, a halogenated group, an aryl group are more preferred. Thereby, it is easy to improve the solvent solubility of the cyanine compound, or it is easy to more finely control the maximum absorption wavelength in the desired wavelength region. The alkyl group contained in the alkyl group, alkoxy group, alkylthio group, and alkoxycarbonyl group is preferably a linear or branched alkyl group. In this case, the number of carbon atoms of the alkyl group, alkoxy group, and alkylthio group is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2, the number of carbon atoms of the alkoxycarbonyl group is preferably 2 to 6, more preferably 2 to 4, further preferably 2 to 3, and the number of carbon atoms of the aryl group and aryloxycarbonyl group is preferably 6 to 12, more preferably 6 to 10. It should be noted that ring A 1 and ring A 2 may also not have the substituent P. When ring A 1 or ring A 2 has the substituent P, the number thereof is preferably 1 to 5, more preferably 1 to 3, further preferably 1 to 2. When ring A 1 or ring A 2 has a plurality of substituents P, the plurality of substituents P may be the same or different.

[0059] Ring A 1 and ring A2 The number of π electrons contained in each of them, that is, the number of π electrons contained in the above aromatic hydrocarbon ring, aromatic heterocyclic ring, or condensed ring containing these ring structures is not particularly limited. For example, it can be 4 or more, or it can be 6 or more. Ring A 1 and Ring A 2 There is no particular limitation on the upper limit of the number of π electrons contained in each of them. Considering the ease of manufacturing the cyanine compound and its solubility in solvents, it is preferably 18 or less, more preferably 14 or less, and further preferably 10 or less. It should be noted that Ring A 1 and Ring A 2 The number of π electrons contained refers to the number of π electrons including the carbon-carbon bond shared with the pyrrole ring in Ring A 1 or Ring A 2 In addition, from the aspect of the ease of manufacturing the cyanine compound, Ring A 1 and Ring A 2 are preferably aromatic hydrocarbon rings, particularly preferably a benzene ring or a naphthalene ring.

[0060] In formula (1), Ring B 1 and Ring B 2 each independently represent a hydrocarbon ring optionally having a substituent and / or a condensed ring structure, or a heterocyclic ring optionally having a substituent and / or a condensed ring structure, and are spiro-bonded to the pyrrole ring represented by the structural formula of formula (1), that is, the pyrrole ring to which the methylene chain L is bonded. For the cyanine compound represented by formula (1), Ring B 1 and Ring B 2 are spiro-bonded to the adjacent pyrrole ring, so that the bonding form of Ring B 1 and Ring B 2 is twisted with respect to the pyrrole ring. As a result, molecular distortion of the cyanine compound occurs, which affects the band gap and enables the absorption wavelength to be extended. The cyanine compound can extend the absorption wavelength by about 30 nm through Ring B 1 and Ring B 2 In addition, the association and aggregation of the cyanine compound are suppressed, and its solubility in organic solvents is improved.

[0061] Examples of the hydrocarbon ring of Ring B 1 and Ring B 2 include aliphatic hydrocarbon rings. For example, they include: monocyclic cycloalkanes having 3 to 10 carbon atoms such as cyclopentane, cyclohexane, and cycloheptane; monocyclic cycloalkenes having 3 to 10 carbon atoms such as cyclopentene, cyclopentadiene, cyclohexene, cyclohexadiene (e.g., 1,3-cyclohexadiene), cycloheptene, and cycloheptadiene. Examples of Ring B 1 and Ring B 2For the heterocyclic ring, ring structures in which one or more carbon atoms constituting the hydrocarbon ring as described above are substituted with at least one atom selected from N (nitrogen atom), S (sulfur atom), and O (oxygen atom) can be cited. For example, furan ring, tetrahydrofuran ring, thiophene ring, tetrahydrothiophene ring, pyrrole ring, pyrrolidine ring, pyrazole ring, oxazole ring, thiazole ring, imidazole ring, pyridine ring, piperidine ring, pyridazine ring, pyrimidine ring, pyrazine ring, pyran ring, tetrahydropyran ring, etc. These hydrocarbon rings and heterocyclic rings may also have a condensed ring structure formed by condensing with other rings. As such ring structures, for example, indene ring, naphthalene ring, anthracene ring, fluorene ring, benzo[b]fluorene ring, indole ring, isoindole ring, benzimidazole ring, quinoline ring, benzopyran ring, acridine ring, xanthene ring, carbazole ring, purine ring, pteridine ring, etc.

[0062] Ring B 1 and Ring B 2 The hydrocarbon ring and heterocyclic ring of may optionally have substituents. As the substituents, organic groups and polar functional groups can be cited. For the details of these organic groups and polar functional groups, refer to the description of the organic groups and polar functional groups of the substituent P above. Among them, as the substituents that Ring B 1 and Ring B 2 optionally has, alkyl, alkoxy, alkylthio, alkoxycarbonyl, aryl, aryloxycarbonyl, halogenated group are preferred, alkyl, alkoxy, alkylthio, halogenated group, aryl are more preferred, and alkyl, alkoxy, halogenated group are further preferred. The alkyl contained in alkyl, alkoxy, alkylthio, and alkoxycarbonyl is preferably a linear or branched alkyl. In this case, the number of carbon atoms of alkyl, alkoxy, and alkylthio is preferably 1 to 8, more preferably 1 to 6, further preferably 1 to 4, and the number of carbon atoms of alkoxycarbonyl is preferably 2 to 8, more preferably 2 to 6, and the number of carbon atoms of aryl and aryloxycarbonyl is preferably 6 to 12, more preferably 6 to 10. It should be noted that Ring B 1 and Ring B 2 may also not have substituents. When Ring B 1 or Ring B 2 has substituents, the number thereof is preferably 1 to 4, more preferably 1 to 3, further preferably 1 to 2. When Ring B 1 or Ring B 2 has a plurality of substituents, the plurality of substituents may be the same or different.

[0063] Ring B 1 and Ring B 2 The ring member number of is not particularly limited. The ring member number of the hydrocarbon ring or heterocyclic ring that is spiro-bonded to the adjacent pyrrole ring is preferably 5 to 8, more preferably 5 to 7, further preferably 5 or 6. If the ring member number of the hydrocarbon ring or heterocyclic ring that is spiro-bonded to the adjacent pyrrole ring of Ring B 1 and Ring B 2 is 5 or 6, then Ring B1 and ring B 2 is easily twisted relative to the pyrrole ring at a larger angle (an angle close to 90°), which can increase the molecular twist of the cyanine compound.

[0064] Regarding ring B 1 and ring B 2 it is preferred that the hydrocarbon ring or heterocyclic ring spiro-bonded to the adjacent pyrrole ring has a π bond. Thus, it is easy to achieve a configuration in which ring B 1 and ring B 2 as a whole is twisted relative to the pyrrole ring, which can increase the molecular twist of the cyanine compound. In this case, it is preferred that the first adjacent atom and the second adjacent atom of the carbon spiro-bonded to the pyrrole ring are connected by a π bond. Examples of the π bond include double bonds, such as a double bond between carbon atoms, a double bond between a carbon atom and a nitrogen atom, and a double bond between nitrogen atoms. Ring B 1 and ring B 2 The π bond of the hydrocarbon ring or heterocyclic ring spiro-bonded to the adjacent pyrrole ring can share a part with the fused ring.

[0065] Regarding ring B 1 and ring B 2 for the hydrocarbon ring or heterocyclic ring spiro-bonded to the adjacent pyrrole ring, it is preferred that the ring member number is 5 or 6 and has a double bond. Examples of such rings include: cyclopentene ring, cyclopentadiene ring, cyclohexene ring, cyclohexadiene ring, 2-pyrroline ring, 3-pyrroline ring, 2H-pyrrole ring, 2-pyrazoline ring, 2-imidazolidine ring, piperazine ring, 2H-pyran ring, 4H-pyran ring, 2H-thiopyran ring, 4H-thiopyran ring, 4H-1,2-oxazine ring, 6H-1,2-oxazine ring, 4H-1,3-oxazine ring, 2H-1,3-oxazine ring, 6H-1,3-oxazine ring, 2H-1,4-oxazine ring, 6H-1,2-thiazine ring, 2H-1,4-thiazine ring, etc.

[0066] Ring B 1 and ring B 2 is preferably a hydrocarbon ring having a fused ring structure or a heterocyclic ring having a fused ring structure. Thus, ring B 1 and ring B 2 is formed in a fluffy state twisted relative to the pyrrole ring, which can increase the molecular twist of the cyanine compound. In this case, in ring B 1 and ring B 2 it is preferred to form a fused ring in such a way as to share the bonds of the first adjacent atom and the second adjacent atom of the carbon spiro-bonded to the pyrrole ring. Thus, ring B 1 and ring B 2 extends further in the direction perpendicular to the plane direction of the pyrrole ring, which can further increase the molecular twist of the cyanine compound.

[0067] Ring B 1With ring B 2 Particularly preferred is a hydrocarbon ring or heterocyclic ring represented by the following formulas (2-1) to (2-4). In the following formulas (2-1) to (2-4), ring C 1 ~ ring C 6 Each independently represents a hydrocarbon ring optionally having a substituent, and Y 1 represents -CH2-, -NH-, -O- or -S-, and Y 2 ~ Y 6 Each independently represents -CH2-, -CH=, -NH-, -N=, -O- or -S-, and * represents the site of spiro bonding to the adjacent pyrrole ring.

[0068] [Chemical formula 6]

[0069]

[0070] If ring B 1 and ring B 2 are a hydrocarbon ring or heterocyclic ring represented by the above formulas (2-1) to (2-4), then ring B 1 and ring B 2 become a hydrocarbon ring or heterocyclic ring having a π bond (double bond) at the first adjacent atom and the second adjacent atom of the carbon atom that is spiro-bonded to the adjacent pyrrole ring and having a fused ring structure that shares a part of the π bond. Therefore, it is easy to achieve an arrangement in which ring B 1 and ring B 2 are twisted as a whole with respect to the pyrrole ring. In addition, ring B 1 and ring B 2 extend further in the direction perpendicular to the plane direction of the pyrrole ring, and the molecular twist of the cyanine compound can be increased.

[0071] As the hydrocarbon ring of ring C 1 ~ ring C 6 , an aromatic hydrocarbon ring and an aliphatic hydrocarbon ring can be cited. For the details of these aromatic hydrocarbon rings and aliphatic hydrocarbon rings, refer to the descriptions of the aromatic hydrocarbon rings of the above ring A 1 and ring A 2 and the aliphatic hydrocarbon rings of ring B 1 and ring B 2 . Ring C 1 ~ ring C 6 is preferably a monocyclic ring. Specifically, it is preferably a monocyclic cycloolefin or benzene ring having 3 to 10 carbon atoms (preferably 5 to 8 carbon atoms), and more preferably a benzene ring (specifically, a benzene ring fused with a 5-membered ring or 6-membered ring that is spiro-bonded at the * position).

[0072] As the substituent optionally possessed by ring C 1 ~ ring C 6 , refer to the above ring B 1 and ring B 2Description of optionally present substituents.

[0073] Y 2 ~Y 6 Each independently represents -CH2-, -CH═, -NH-, -N═, -O- or -S-. It should be noted that preferably, oxygen atoms are not bonded to each other, and preferably, sulfur atoms are not bonded to each other.

[0074] As Y 2 -Y 3 Specific examples of can be listed as: -CH2-CH2-, -CH═CH-, -CH2-NH-, -NH-CH2-, -CH═N-, -N═CH-, -N═N-, -CH2-O-, -O-CH2-, -CH2-S-, -S-CH2-, -NH-O-, -O-NH-, -NH-S-, -S-NH-, -O-S-, -S-O-, etc. Among them, Y 2 and Y 3 are preferably connected by a π bond (double bond), and Y 2 -Y 3 is preferably -CH═CH-, -CH═N-, -N═CH-.

[0075] As Y 4 -Y 5 -Y 6Specific examples include: -CH2-CH2-CH2-, -CH2-CH=CH-, -CH=CH-CH2-, -NH-CH2-CH2-, -CH2-NH-CH2-, -CH2-CH2-NH-, -NH-CH2-NH-, -NH-CH=CH-, -CH=CH-NH-, -CH2-N=CH-, -CH2-CH=N-, -CH=N-CH2-, -NH-N=CH-, -NH-CH=N-, -CH=N-NH-, -N=CH-NH-, -N=N-NH-, -NH-N=N-, -O-CH2-CH2-, -CH2-O-CH2-, -CH2-CH2-O-, -O-CH2-O-, -O-CH2-NH-, -O-NH-CH2-, -O-CH=CH-, -O-CH=N-, -O-N=CH-, -O-NH-NH-, -NH-O-CH2-, -CH2-O-NH-, -NH-O-NH-, -CH2-NH-O-, -NH-CH2-O-, -CH=CH-O-, -CH=N-O-, -N=CH-O-, -NH-NH-O-, -O-NH-O-, -O-N=N-, -N=N-O-, -S-CH2-CH2-, -CH2-S-CH2-, -CH2-CH2-S-, -S-CH2-S-, -S-CH2-NH-, -S-NH-CH2-, -S-CH=CH-, -S-CH=N-, -S-N=CH-, -S-NH-NH-, -NH-S-CH2-, -CH2-S-NH-, -NH-S-NH-, -CH2-NH-S-, -NH-CH2-S-, -CH=CH-S-, -CH=N-S-, -N=CH-S-, -NH-NH-S-, -S-NH-S-, -S-N=N-, -N=N-S-, -O-S-CH2-, -S-O-CH2-, -CH2-O-S-, -CH2-S-O-, -O-CH2-S-, -S-CH2-O-, -O-S-NH-, -S-O-NH-, -NH-O-S-, -NH-S-O-, -O-NH-S-, -S-NH-O-, -O-S-O-, -S-O-S, etc. Among them, Y 5 and Y 6 are preferably connected by a π bond (double bond), and Y 5 -Y 6 is preferably -CH=CH-, -CH=N-, -N=CH-. If it is Y 4 -Y 5 -Y 6, it is preferred that -CH2-CH=CH-, -NH-CH=CH-, -CH2-N=CH-, -CH2-CH=N-, -NH-N=CH-, -NH-CH=N-, -NH-N=N-, -O-CH=CH-, -O-CH=N-, -O-N=CH-, -O-N=N-, -S-CH=CH-, -S-CH=N-, -S-N=CH-, -S-N=N-.

[0076] In formula (1), R 1 and R 2 each independently represent an organic group. For the details of the organic groups of R 1 and R 2 , refer to the description of the organic groups of the substituent P above. Among them, R 1 and R 2 are preferably alkyl, alkoxy, aryl, aralkyl, more preferably alkyl, aralkyl, and further preferably alkyl. In this case, the number of carbon atoms of the alkyl and alkoxy is preferably 1 to 8, more preferably 1 to 5, and further preferably 1 to 3. The number of carbon atoms of the aryl is preferably 6 to 12, more preferably 6 to 10, and the number of carbon atoms of the aralkyl is preferably 7 to 13, more preferably 7 to 11.

[0077] In formula (1), L represents a methylene chain having 5 or more and 9 or less carbon atoms, that is, a methylene chain in which 5 or more and 9 or less methylene groups (-CH=) are bonded to form a conjugated double bond. The methylene groups contained in the methylene chain may each independently have a substituent, that is, the hydrogen atoms on the methylene groups may each independently be substituted by a substituent. In addition, the substituents may optionally be linked to each other. Examples of the substituent that the methylene group may optionally have include an organic group and a polar functional group. For the details of these organic groups and polar functional groups, refer to the description of the organic groups and polar functional groups of the substituent P above. It should be noted that when the methylene group contained in the methylene chain has a substituent, the number of carbon atoms of the methylene chain refers to the number of carbon atoms excluding the substituent.

[0078] The methylene chain L is preferably a group formed by connecting an odd number of methylene groups. Therefore, the methylene chain preferably has 5, 7, or 9 carbon atoms, and is preferably a group formed by connecting 5, 7, or 9 methylene groups. In this case, the cyanine compound represented by formula (1) is a compound represented by the following formula (1-1) to formula (1-3). In formula (1-1) to formula (1-3), R 11 to R 19 each independently represent a hydrogen atom, an organic group, or a polar functional group.

[0079] [Chemical formula 7]

[0080]

[0081] As substituents optionally possessed by the methylene group, alkyl, alkoxy, aryl, aralkyl, aryloxy, alkylsulfonyl, arylsulfonyl, amino, amido, and halo groups are preferred. In this case, the number of carbon atoms of the alkyl, alkoxy, and alkylsulfonyl groups is preferably 1 to 8, more preferably 1 to 5, and still more preferably 1 to 3. The number of carbon atoms of the aryl, aryloxy, and arylsulfonyl groups is preferably 6 to 12, more preferably 6 to 10. The number of carbon atoms of the aralkyl group is preferably 7 to 13, more preferably 7 to 11. The amino group is preferably an amino group represented by the formula: -NR a1 R a2 wherein R a1 and R a2 are each independently a hydrogen atom, an alkyl group, or an aryl group. The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms of the aryl group is preferably 6 to 12, more preferably 6 to 10. The hydrogen atoms of the alkyl and aryl groups may be substituted by halo groups. The amino group may be an amino group represented by the formula: -NR a1 R a2 wherein R a1 and R a2 are linked to form a ring. The number of ring members of the ring is preferably 5 or 6. The atoms constituting the ring are preferably carbon atoms, oxygen atoms, and sulfur atoms in addition to the nitrogen atom. The amido group is preferably an amido group represented by the formula: -NR a5 -C(=O)-R a6 wherein R a5 and R a6 are each independently a hydrogen atom, an alkyl group, or an aryl group. The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3. The number of carbon atoms of the aryl group is preferably 6 to 12, more preferably 6 to 10. The hydrogen atoms of the alkyl and aryl groups may be substituted by halo groups.

[0082] When the substituents possessed by the methylene groups are linked to each other, it is preferred that the substituents possessed by the second adjacent methylene group are linked to each other to form a ring. In formulas (1-1) to (1-3), it is preferred that R 11 and R 13 , R 12 and R 14 , R 13 and R 15 , R 14 and R 16 , R 15 and R 17 , R 16 and R 18 or R 17 and R 19 are linked to each other to form a ring.

[0083] The ring formed by linking the substituents of the methylene group is preferably a 5- to 8-membered ring, more preferably a 5- to 7-membered ring, and still more preferably a 5-membered or 6-membered ring. The ring formed by linking the substituents of the methylene group is formed by sharing a part with the methylene chain, but may have an unsaturated bond or may not have an unsaturated bond except for the part shared with the methylene chain. Preferably, the ring formed by linking the substituents of the methylene group does not have an unsaturated bond except for the part shared with the methylene chain.

[0084] The ring formed by linking the substituents of the methylene group may optionally have a substituent. Examples of such substituents include organic groups and polar functional groups. For the details of these organic groups and polar functional groups, refer to the description of the organic groups and polar functional groups of the above-mentioned substituent P. Among them, as the substituent, an alkyl group, an alkoxy group, an aryl group, an amino group, and a halogenated group are preferred. In this case, the number of carbon atoms of the alkyl group and the alkoxy group is preferably 1 to 5, more preferably 1 to 3, still more preferably 1 or 2, and the number of carbon atoms of the aryl group is preferably 6 to 12. The amino group is preferably an amino group represented by the formula: -NR a1 R a2 , where R a1 and R a2 are each independently a hydrogen atom, an alkyl group or an aryl group. The number of carbon atoms of the alkyl group is preferably 1 to 5, more preferably 1 to 3, and the number of carbon atoms of the aryl group is preferably 6 to 12, more preferably 6 to 10.

[0085] The substituent that the methylene group may optionally have is preferably bonded to the median (central) methylene group or the methylene group adjacent to the median. The other methylene groups preferably do not have a substituent. In formula (1-1), R 12 to R 14 can be a hydrogen atom, an organic group or a polar functional group, and R 11 and R 15 are preferably hydrogen atoms. In formula (1-2), R 13 to R 15 can be a hydrogen atom, an organic group or a polar functional group, and R 11 , R 12 , R 16 , R 17 are preferably hydrogen atoms. In formula (1-3), R 14 to R 16 can be a hydrogen atom, an organic group or a polar functional group, and R 11 to R 13 , R 17 to R 19Preferably a hydrogen atom. More preferably, the substituent that does not form a ring by bonding is bonded to the methine group at the meso-position, the substituent that forms a ring by bonding is bonded to the methine group adjacent to the meso-position and is bonded to each other. In addition, the methine chain L also preferably has no substituent.

[0086] In formula (1), X - represents a monovalent anion having a pKa of the conjugate acid of -8.0 or less. In the cyanine compound of the present invention, a salt is formed between the cation having the above cyanine skeleton and a monovalent anion having a pKa of the conjugate acid of -8.0 or less. Thus, in combination with the cyanine compound having ring B 1 and ring B 2 can improve the solubility in organic solvents. In addition, the heat resistance of the cyanine compound can also be improved.

[0087] Examples of the acid having a pKa of -8.0 or less include the acids having a pKa of -8.0 or less described in Table 1 of Agnes Kutt et al., “Equilibrium Acidities of Superacids”, J. Org. Chem., 2011, 76, 391-395. When the pKa is known in the literature or the like, the value is cited, and when it is not known, the calculated value obtained using Advanced Chemistry Development (ACD / Labs) Software can be adopted. The pKa of the conjugate acid of the anion of X - is preferably -10.0 or less, more preferably -11.0 or less, and further preferably -18.0 or less. The anion of X - is preferably a low nucleophilicity anion, and is preferably an anion formed by dissociating a proton from an acid having a low pKa, generally called a super acid.

[0088] As the anion of X - , for example, anions represented by the following formulas (3-1) to (3-3) can be cited. In formulas (3-1) to (3-3), R 21 to R 27 each independently represent a fluorine atom, a fluoroalkyl group, a fluoroaryl group or a cyano group, and R 28 and R 29 each independently represent a fluorine atom, a fluoroalkyl group, a fluoroaryl group, a cyano group or -SO2-R 30 , and R 30 represents a fluorine atom, a fluoroalkyl group, a fluoroaryl group or a cyano group.

[0089] [Chemical formula 8]

[0090]

[0091] In addition, X -The anion can also be a perchlorate ion, a fluorosulfate ion, a fluoroalkylsulfonate ion, a cyanoalkylsulfonate ion, a 2,4,6-trinitrobenzenesulfonate ion, a 1,1,3,3-tetracyanoallyl ion, a fluorophosphate ion, a fluoroantimonate ion, etc., in addition to the anions of formula (3-1) to formula (3-3).

[0092] In formula (3-1) to formula (3-3), R 21 ~R 30 The fluoroalkyl groups may include linear, branched or cyclic fluoroalkyl groups, preferably linear or branched, more preferably linear. The number of carbon atoms of the fluoroalkyl group is preferably 1 to 8, more preferably 1 to 6, further preferably 1 to 4, and in addition, a perfluoroalkyl group is preferred. R 21 ~R 30 The fluoroaryl groups preferably have 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms, and in addition, a perfluoroaryl group is preferred. In addition, among the above, the fluoroalkylsulfonate ion, the fluorophosphate ion, and the fluoroantimonate ion listed as anions other than the anions of formula (3-1) to formula (3-3) are preferably a perfluoroalkylsulfonate ion, a hexafluorophosphate ion, and a hexafluoroantimonate ion, respectively. The number of carbon atoms of the alkyl group of the fluoroalkylsulfonate ion is preferably 1 to 8, more preferably 1 to 6, further preferably 1 to 4.

[0093] X - The anion of is preferably an anion represented by formula (3-1), i.e., a borate ion, whereby the solubility of the cyanine compound in an organic solvent can be further improved. In this case, R 21 ~R 24 are more preferably a fluoroalkyl group, a fluoroaryl group or a cyano group, further more preferably a fluoroalkyl group or a fluoroaryl group, and particularly preferably a fluoroaryl group. Examples of the borate ion having a pKa of the conjugate acid of -8.0 or less and having a fluoroaryl group include a tetrakis(pentafluorophenyl)borate anion (the pKa of the conjugate acid is about -30).

[0094] The cyanine compound of the present invention preferably has a maximum absorption peak in the range of 650 nm to 1100 nm in the absorption spectrum measured in methanol in the wavelength range of 600 nm to 1300 nm. That is, when the absorption spectrum of the cyanine compound is measured in methanol, it preferably has an absorption peak having a maximum absorption in the range of 650 nm to 1100 nm, and the maximum absorption of the absorption peak takes the maximum value in the wavelength range of 600 nm to 1300 nm. It should be noted that the maximum absorption wavelength of the maximum absorption peak is referred to as λmax. The maximum absorption wavelength (λmax) is more preferably 655 nm or more, further more preferably 1200 nm or less, further preferably 1100 nm or less, and further more preferably 1000 nm or less.

[0095] The cyanine compound of the present invention can have a new absorption peak in the near-infrared region in a cured resin composition. For example, the cyanine compound of the present invention can exhibit a maximum absorption peak in the near-infrared region (for example, in the range of wavelengths from 650 nm to 1100 nm) in a solution or an uncured resin composition. In the cured resin composition, in addition to the maximum absorption peak, a new absorption peak can also be exhibited on the longer wavelength side (for example, in the range of wavelengths from 800 nm to 1100 nm). Therefore, a filter having a resin layer formed by curing a resin composition containing the cyanine compound can absorb light in a wide wavelength range in the near-infrared region and can be applied to a multi-band filter having a plurality of absorption bands in the near-infrared region (for example, in the wavelength range of 650 nm to 1200 nm). It should be noted that the cured resin composition can be a resin composition cured by heating, a resin composition cured by cooling, a resin composition cured by solvent evaporation, or a resin composition cured by reaction. The reason for the appearance of the new absorption peak of the cyanine compound in the cured resin composition is not yet certain, but it is speculated that in the cured resin composition, the cyanine compounds form H-associates, J-associates or associates similar to them with each other, or the cyanine compounds interact with each other to form a charge transfer complex, thereby causing changes such as activation of forbidden transitions.

[0096] The cyanine compound of the present invention can be produced by reacting a nitrogen-containing heterocyclic compound represented by the following formula (4), or further reacting a nitrogen-containing heterocyclic compound in which ring A 1 is ring A 2 , ring B 1 is ring B 2 , R 1 is R 2 with a polymethine compound, and performing anion exchange as needed. In the nitrogen-containing heterocyclic compound, ring A 1 , ring A 2 , ring B 1 , ring B 2 , R 1 and R 2 have the same meanings as in the above formula (1), and Z - represents a monovalent anion. If a nitrogen-containing heterocyclic compound represented by formula (4) is used as a reaction raw material or intermediate, the cyanine compound of formula (1) can be easily produced. Therefore, the present invention also provides a nitrogen-containing heterocyclic compound represented by the following formula (4).

[0097] [Chemical formula 9]

[0098]

[0099] The polymethine compound reacting with the above nitrogen-containing heterocyclic compound preferably has groups capable of reacting with the above nitrogen-containing heterocyclic compound at both ends. As the reactive group, an amino group can be cited. The amino group preferably has a π-conjugation with the methine chain of the polymethine compound. As such an amino group, an aromatic amino group is preferably cited. Therefore, the polymethine compound preferably has aromatic amino groups at both ends. The methyl group bonded to the second carbon atom of the pyrrole ring of the nitrogen-containing heterocyclic compound of the formula (4) is bonded to the carbon atom adjacent to the amino group bonded to both ends of the polymethine compound, thereby forming the cationic part of the cyanine compound of the formula (1).

[0100] In the formula (4), Z - can be the same as X - in the above formula (1). In this case, by reacting the nitrogen-containing heterocyclic compound with the polymethine compound, the cyanine compound of the formula (1) can be obtained without anion exchange. It should be noted that the pKa of the conjugate acid of Z - is preferably greater than the pKa of the conjugate acid of X - , or preferably greater than -8.0. Thereby, the cyanine compound of the present invention can be efficiently produced. Therefore, it is preferred to react the nitrogen-containing heterocyclic compound with the polymethine compound and then anion-exchange Z - to X - thereby producing the cyanine compound of the formula (1).

[0101] From the aspect of the ease of production of the nitrogen-containing heterocyclic compound of the formula (4), Z - is preferably a halide ion or a sulfonate ion. As the halide ion, fluoride ion, chloride ion, bromide ion, iodide ion, etc. can be cited. The sulfonate ion is preferably a sulfonate ion represented by the formula: R b -SO3 - , wherein R b is an alkyl group, an aryl group or an alkoxy group. The alkyl group preferably has 1 to 5 carbon atoms, more preferably 1 to 3 carbon atoms. The aryl group preferably has 6 to 12 carbon atoms, more preferably 6 to 10 carbon atoms. The aralkyl group preferably has 7 to 13 carbon atoms, more preferably 7 to 11 carbon atoms. The aryl group contained in the aryl group and aralkyl group of R b optionally has a substituent. As the substituent, alkyl group, alkoxy group, alkylthio group, alkoxycarbonyl group, halogenated group, nitro group, etc. can be cited. Among them, Z - is preferably a halide ion, more preferably a bromide ion or an iodide ion, and further preferably an iodide ion.

[0102] The present invention also provides a method for manufacturing a nitrogen-containing heterocyclic compound, which includes a step of reacting a compound represented by the following formula (5) with an alkylating agent represented by the following formula (6) to obtain a compound represented by formula (4). In the following formulas (4) to (6), ring A 1 、ring B 1 and Z - represent the same meanings as those in the above formulas (1) and (4), and R 1 represents an alkyl group. Z in formula (6) represents an atom or group that provides a monovalent anion, and by detaching from R 1 -Z, a monovalent anion Z - is generated.

[0103] [Chemical formula 10]

[0104]

[0105] By reacting the compound of formula (5) with the alkylating agent of formula (6), the alkyl group of the alkylating agent of formula (6) undergoes an electrophilic reaction on the nitrogen atom of the pyrrole ring of the compound of formula (5), thereby introducing an alkyl group onto the nitrogen atom. Thus, the nitrogen-containing heterocyclic compound of formula (4) can be easily manufactured.

[0106] In the alkylating agent of formula (6), the alkyl group of R 1 is preferably linear or branched, more preferably linear. The number of carbon atoms of the alkyl group of R 1 is preferably 1 to 8, more preferably 1 to 5, and further preferably 1 to 3. The alkyl group of R 1 is particularly preferably a methyl group.

[0107] As the alkylating agent, a known alkylating agent can be used, and a halogenated alkane or an alkyl sulfonate is preferably used. In this case, Z is a halogen atom or a group represented by R b -SO3-, and the alkyl sulfonate is a substance represented by R b -SO2-OR 1 . For the details of R b , refer to the above description.

[0108] The alkylating agent of formula (6) is preferably a halogenated methane or methyl sulfonate. As the methyl sulfonate, methyl methanesulfonate, methyl benzenesulfonate, methyl p-toluenesulfonate, etc. can be cited. In this case, the R 1 of the nitrogen-containing heterocyclic compound of formula (4) is a methyl group, and Z - is a halide ion or a sulfonate ion.

[0109] The compound of formula (5) can be manufactured, for example, by reacting a hydrazine hydrochloride represented by the following formula (7) with an acetyl compound represented by the following formula (8). In the following formulas (5), (7), and (8), ring A1 and ring B 1 represent the same meanings as these in the above formula (1).

[0110] [Chemical formula 11]

[0111]

[0112] By reacting a hydrazine hydrochloride (compound of the above formula (7)) of an aromatic hydrocarbon ring, an aromatic heterocyclic ring, or a condensed ring containing these ring structures with an acetyl compound (compound of the above formula (8)) bonded with a hydrocarbon ring or a heterocyclic ring, a nitrogen-containing heterocyclic compound of formula (5) can be produced. The synthesis of the nitrogen-containing heterocyclic compound of formula (5) can also refer to the following paper: Sajjadi et al., “New 3H-Indole Synthesis by Fischer's Method. Part I”, Molecules, vol. 15, p. 2491 - 2498 (2010).

[0113] The cyanine compound of the present invention has excellent solubility in solvents. Therefore, the present invention also provides a cyanine compound solution containing the cyanine compound represented by formula (1) and a solvent. The cyanine compound solution can be applied to, for example, anti-counterfeiting ink liquids and can be used as an ink liquid composition. As the solvent, an organic solvent is preferably used, and thus a cyanine compound solution in which the cyanine compound is dissolved at a higher concentration than before can be obtained. Such a cyanine compound solution and ink liquid composition can efficiently absorb light in the near-infrared region.

[0114] Examples of the solvent for the cyanine compound solution include: ketones such as methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; esters such as ethyl acetate, propyl acetate, and butyl acetate; ethers such as tetrahydrofuran, dioxane, diethyl ether, and dibutyl ether; alcohols such as methanol, ethanol, and isopropyl alcohol; glycol derivatives (ether compounds, ester compounds, ether ester compounds, etc.) such as PGMEA (2-acetoxy-1-methoxypropane), ethylene glycol monobutyl ether, ethylene glycol monoethyl ether, and ethylene glycol ethyl ether acetate; amides such as N,N-dimethylacetamide; pyrrolidones such as N-methyl-pyrrolidone; aromatic hydrocarbons such as toluene and xylene. These solvents can be used alone or in combination of two or more. Among them, ketones, alcohols, glycol derivatives, and aromatic hydrocarbons are particularly preferred.

[0115] The amount of the solvent used can be appropriately set according to the desired concentration of the cyanine compound in the cyanine compound solution. The concentration of the cyanine compound in the cyanine compound solution can be appropriately set, for example, in the range of 0.01 - 10% by mass, and the concentration can be 0.1% by mass or more or 0.5% by mass or more, and can also be 5% by mass or less or 3% by mass or less.

[0116] The cyanine compound of the present invention contained in the cyanine compound solution may be only one kind or two or more kinds. The cyanine compound solution may contain other pigments together with the cyanine compound of the present invention. For example, it may contain at least one selected from near-infrared absorbing pigments, visible light absorbing pigments, and ultraviolet absorbing pigments. For the details of the near-infrared absorbing pigment, visible light absorbing pigment, and ultraviolet absorbing pigment, refer to the description of the near-infrared absorbing pigment, visible light absorbing pigment, and ultraviolet absorbing pigment that can be contained in the resin composition described later.

[0117] The cyanine compound of the present invention can be mixed with a resin component to form a resin composition. The resin composition is a resin composition containing at least the cyanine compound of the present invention and a resin component. The resin composition of the present invention can be preferably applied to a filter, for example, by forming a resin molded body such as a film. In addition, the resin molded body can also be applied to a near-infrared absorbing film for blocking heat rays for energy saving, a near-infrared absorbing plate, a material for a solar cell using visible light and near-infrared light, a plasma display panel (PDP), a specific wavelength absorbing filter for a CCD, etc.

[0118] The cyanine compound of the present invention has excellent solubility in an organic solvent. Therefore, when manufacturing the resin composition, by dissolving the cyanine compound in an organic solvent to prepare a cyanine compound solution and mixing it with the resin component, the cyanine compound can be easily present uniformly and at a high concentration in the resin composition. In addition, the cyanine compound of the present invention has excellent heat resistance. Therefore, for example, even when compounded in a thermoplastic resin or a thermosetting resin and heated and molded or thermoset, a cured product that can preferably absorb light in the near-infrared region derived from the cyanine compound can be obtained.

[0119] The resin composition of the present invention and its cured product can also be applied to the welding of resins using the laser welding method. For example, it can be contained and used in the resin to be welded, or used as an absorber of laser light. The joining of resins using the laser welding method can be carried out by overlapping a light-transmitting resin that transmits laser light and a light-absorbing resin that absorbs laser light and irradiating laser light from the light-transmitting resin side. The irradiated laser light transmits through the light-transmitting resin, absorbs energy on the surface of the light-absorbing resin and generates heat, thereby melting the light-absorbing resin. Furthermore, the light-transmitting resin is also melted by heat conduction, and the two resins are welded. As the light-absorbing resin, a colored resin containing carbon black, a black dye, etc. is sometimes used. However, since a laser having a wavelength of 800 nm to 1300 nm (for example, a semiconductor laser, a YAG laser, a fiber laser) is used in laser welding, by forming a light-absorbing resin from the resin composition of the present invention, laser welding of transparent resins can be achieved. That is, the cyanine compound of the present invention can function as an absorption material of laser light, that is, a heat source. In the laser welding method, the resin composition of the present invention can also be used as an absorber of laser light sandwiched between two light-transmitting resins.

[0120] The resin composition of the present invention and its cured product can also be applied to materials for photofixing methods using light that is not easily affected by pressure or heating (electrostatic development toners for flash fixing methods), cosmetic materials having a function of absorbing or blocking near-infrared rays, materials for light detection and ranging (LIDAR) systems, and the like.

[0121] The cyanine compound of the present invention contained in the resin composition may be only one kind, or two or more kinds. As long as the resin composition ensures the desired properties corresponding to the use, it may also contain other pigments together with the cyanine compound of the present invention. For example, it may contain at least one selected from near-infrared absorbing pigments, visible light absorbing pigments, and ultraviolet absorbing pigments.

[0122] If the resin composition further contains a near-infrared absorbing pigment and / or a visible light absorbing pigment, a filter having light selective transmissivity can be obtained from the resin composition. For example, when the resin composition contains the cyanine compound of the present invention and a near-infrared absorbing pigment, the transmission of light in a wide range from red to near-infrared regions can be suppressed, and it can be used as a resin composition for a filter that preferentially transmits light in the visible light region. When the resin composition contains the cyanine compound of the present invention and a visible light absorbing pigment, it can be used as a resin composition for a color filter, a blue light reduction filter, and the like.

[0123] The near-infrared absorbing pigment preferably has a maximum absorption in the wavelength range of 600 nm to 1100 nm. More preferably, in the absorption spectrum of the near-infrared region pigment in the wavelength range of 450 nm to 1100 nm, it has a peak having a maximum absorption in the wavelength range of 600 nm to 1100 nm, and the maximum absorption of the absorption peak takes the maximum value in the wavelength range of 450 nm to 1100 nm. The maximum absorption wavelength is more preferably 630 nm or more, further preferably 660 nm or more, and furthermore preferably 1000 nm or less, and further preferably 950 nm or less.

[0124] As the visible light absorbing pigment, any pigment having a maximum absorption peak at a maximum absorption wavelength in the visible light region (for example, in the range where the wavelength exceeds 420 nm and is less than 680 nm) can be used without particular limitation. Among them, as the visible light absorbing pigment, a pigment having a maximum absorption peak at a maximum absorption wavelength in the range of 500 nm or more and less than 680 nm, where the visibility is high, is preferably used.

[0125] The near-infrared absorbing pigment and the visible light absorbing pigment may be an organic pigment, an inorganic pigment, or an organic-inorganic composite pigment (for example, an organic compound coordinated with a metal atom or ion), and there is no particular limitation. Examples of the near-infrared absorbing pigment and the visible light absorbing pigment include: cyanine-based pigments other than the cyanine compounds of the present invention, squarylium-based pigments, croconium-based pigments, cyclic tetrapyrrole-based pigments (for example, porphyrins, chlorins, phthalocyanines, naphthalocyanines, corphins, etc.) optionally having copper (for example, Cu(II)), zinc (for example, Zn(II)), etc. as central metal ions, azo-based pigments, quinone-based pigments, xanthene-based pigments, indoline-based pigments, arylmethane-based pigments, quaterrylene-based pigments, diimonium-based pigments, perylene-based pigments, quinacridone-based pigments, oxazine-based pigments, dipyrromethene-based pigments, nickel complex-based pigments, copper ion-based pigments, etc. These pigments may be used alone or in combination of two or more. Among them, as the near-infrared absorbing pigment and the visible light absorbing pigment, from the aspect of effectively absorbing light of a desired wavelength, it is preferable to use at least one selected from squarylium-based pigments, croconium-based pigments, phthalocyanine-based pigments, cyanine-based pigments other than the cyanine compounds of the present invention, and dipyrromethene-based pigments. As the near-infrared absorbing pigment, it is preferable to use at least one selected from squarylium-based pigments, croconium-based pigments, phthalocyanine-based pigments, and cyanine-based pigments other than the cyanine compounds of the present invention. Thereby, it is easy to effectively absorb light in the near-infrared region and improve the visible light transmittance.

[0126] The resin composition may also contain an ultraviolet absorbing pigment. The ultraviolet absorbing pigment preferably has a maximum absorption in the range of 300 nm to 400 nm, for example. By the resin composition containing the ultraviolet absorbing pigment, a filter having a light selective transmittance in which the transmission of light in the ultraviolet to purple region is suppressed can be obtained from the resin composition. In addition, deterioration of the resin composition caused by light in the ultraviolet to purple region can be suppressed, or even when the resin composition is exposed to ultraviolet light during storage, or during the manufacture / processing (for example, evaporation coating, installation, etc.) of the filter, deterioration of the resin component and other components such as the cyanine compound contained in the resin composition caused by the ultraviolet light can be suppressed.

[0127] As the ultraviolet absorbing pigment, known ultraviolet absorbers such as benzotriazole compounds, benzophenone compounds, salicylic acid compounds, benzoxazinone compounds, cyanoacrylate compounds, benzoxazole compounds, merocyanine compounds, and triazine compounds can be used. Only one kind of ultraviolet absorbing pigment can be used, or two or more kinds can be used. The ultraviolet absorbing pigment (ultraviolet absorber) can be a commercially available substance. For example, the ADK STAB (registered trademark) series manufactured by ADEKA Corporation, the TINUVIN (registered trademark) series manufactured by BASF Corporation, the ZISLIZER (registered trademark) series manufactured by Sankyo Kasei Co., Ltd., the SUMISORB (registered trademark) series manufactured by Sumitomo Chemical Co., Ltd., the VIOSORB (registered trademark) series manufactured by Kyodo Yakuhin Co., Ltd., the SEESORB (registered trademark) series manufactured by SHIPRO KASEI Kaisha, Ltd., etc. can be used. In addition, the ethylene compounds disclosed in JP-A-2019-014707 and JP-A-2022-158995 can also be used as the ultraviolet absorbing pigment.

[0128] From the aspect of exhibiting the desired performance, the content of the cyanine compound in the resin composition is preferably 0.01% by mass or more, more preferably 0.03% by mass or more, and still more preferably 0.1% by mass or more based on 100% by mass of the solid content of the resin composition. In addition, from the aspect of improving the moldability, film-forming property, etc. of the resin composition, the content of the cyanine compound in the resin composition is preferably 25% by mass or less, more preferably 20% by mass or less, and still more preferably 15% by mass or less based on 100% by mass of the solid content of the resin composition. When the resin composition further contains other pigments, their total content is preferably within the above range. It should be noted that the solid content amount of the resin composition refers to the amount of the resin composition after removing the solvent when the resin composition contains a solvent.

[0129] As the resin component contained in the resin composition, known resins can be used. As the resin component, a resin component having high transparency and capable of dissolving the cyanine compound of the present invention is preferred. When other pigments are used in combination, it is preferred that the resin component can also dissolve other pigments. By selecting such a resin component, high transmittance in the wavelength region to be transmitted and high absorbency in the wavelength region to be blocked can be achieved at the same time.

[0130] As the resin component, not only the polymerized resin can be used, but also resin raw materials (including precursors of resins, raw materials of the precursors, monomers constituting the resin, etc.) can be used, and the resin raw materials are polymerized or crosslinked during the molding of the resin composition and embedded in the resin. In the present invention, any resin is included in the resin component. It should be noted that in the latter case, unreacted substances, reactive terminal functional groups, ionic groups, catalysts, acid / basic groups, etc. present in the reaction solution obtained by the polymerization reaction may decompose part or all of the structure of the cyanine compound. Therefore, in such a case where there is such a concern, it is desirable to incorporate the cyanine compound into the polymerized resin to form a resin composition.

[0131] As the resin component, a resin with high transparency is preferably used, whereby the light selective absorption characteristics of the cyanine compound contained in the resin composition can be appropriately and effectively utilized. The resin component can be, for example, a thermoplastic resin or a thermosetting resin. Examples of the resin component include: (meth)acrylic resins, (meth)acrylic urethane resins, polyvinyl chloride resins, polyvinylidene chloride resins, polyolefin resins (e.g., polyethylene resins, polypropylene resins), cycloolefin resins, melamine resins, polyurethane resins, styrene resins, polyvinyl acetate, polyamide resins (e.g., nylon), aramid resins, polyimide resins, polyamideimide resins, alkyd resins, phenolic resins, epoxy resins, polyester resins (e.g., polybutylene terephthalate (PBT) resins, polyethylene terephthalate (PET) resins, polyarylate resins, etc.), polysulfone resins, butyral resins, polycarbonate resins, polyether resins, ABS resins (acrylonitrile-butadiene-styrene resins), AS resins (acrylonitrile-styrene copolymers), silicone resins, modified silicone resins (e.g., (meth)acrylic silicone resins, alkyl polysiloxane resins, silicone polyurethane resins, silicone polyester resins, silicone acrylic resins, etc.), fluorine-based resins (e.g., fluorinated aromatic polymers, polytetrafluoroethylene (PTFE), perfluoroalkoxy fluororesin (PFA), fluorinated polyarylether ketone (FPEK), fluorinated polyimide (FPI), fluorinated polyamic acid (FPAA), fluorinated polyether nitrile (FPEN), etc.). Among them, from the viewpoints of excellent transparency and heat resistance, polyimide resins, polyamideimide resins, (meth)acrylic resins, cycloolefin resins, epoxy resins, polyester resins, polyarylate resins, polyamide resins, polycarbonate resins, polysulfone resins, and fluorinated aromatic polymers are preferred.

[0132] Polyimide resin is a polymer containing imide bonds in the repeating units of the main chain. For example, polyamic acid can be obtained by polycondensing tetracarboxylic dianhydride and diamine, and then dehydrating / cyclizing (imide-forming) it to produce polyimide resin. As the polyimide resin, aromatic polyimide in which aromatic rings are linked by imide bonds is preferably used. Examples of polyimide resins that can be used include: NEOPULIM (registered trademark) manufactured by Mitsubishi Gas Chemical Company, Kapton (registered trademark) manufactured by DuPont, AURUM (registered trademark) manufactured by Mitsui Chemicals, Meldin (registered trademark) manufactured by Saint-Gobain, TPS (registered trademark) TI3000 series manufactured by Toray Plastics Precision, etc.

[0133] Polyamideimide resin is a polymer containing amide bonds and imide bonds in the repeating units of the main chain. Examples of polyamideimide resins that can be used include: Torlon (registered trademark) manufactured by Solvay Advanced Polymers, Vylomax (registered trademark) manufactured by Toyobo, TPS (registered trademark) TI5000 series manufactured by Toray Plastics Precision, etc.

[0134] (Meth)acrylic resin is a polymer having repeating units derived from (meth)acrylic acid or its derivatives. For example, resins having repeating units derived from (meth)acrylate such as poly(meth)acrylate resin are preferably used. The (meth)acrylic resin preferably has a ring structure in the main chain. Examples include: ring structures containing carbonyl groups such as lactone ring structure, glutaric anhydride structure, glutarimide structure, maleic anhydride structure, maleimide ring structure, etc.; ring structures not containing carbonyl groups such as oxetane ring structure, azetidine ring structure, tetrahydrofuran ring structure, pyrrolidine ring structure, tetrahydropyran ring structure, piperidine ring structure, etc. It should be noted that the ring structures containing carbonyl groups also include structures containing carbonyl derivative groups such as imide groups. Examples of (meth)acrylic resins having a ring structure containing carbonyl groups include those described in Japanese Patent Application Laid-Open No. 2004-168882, Japanese Patent Application Laid-Open No. 2008-179677, International Publication No. 2005 / 54311, Japanese Patent Application Laid-Open No. 2007-31537, etc.

[0135] The cycloolefin resin is a polymer obtained by using cycloolefins as at least a part of monomer components and polymerizing them, and there is no particular limitation as long as it is a resin having an alicyclic structure in a part of the main chain. As the cycloolefin resin, for example, TOPAS (registered trademark) manufactured by POLYPLASTICS Co., Ltd., APEL (registered trademark) manufactured by Mitsui Chemicals, Inc., ZEONEX (registered trademark) and ZEONOR (registered trademark) manufactured by Nippon Zeon Co., Ltd., ARTON (registered trademark) manufactured by JSR Corporation, etc. can be used.

[0136] Epoxy resin is a resin that can be cured by crosslinking an epoxide compound (prepolymer) in the presence of a curing agent and a curing catalyst. Examples of the epoxide compound include aromatic epoxide compounds, aliphatic epoxide compounds, alicyclic epoxide compounds, hydrogenated epoxide compounds, etc. For example, fluorene-based epoxy resin (OGSOL (registered trademark) PG-100) manufactured by Osaka Gas Chemicals Co., Ltd., bisphenol A type epoxide compound (JER (registered trademark) 828EL) manufactured by Mitsubishi Chemical Corporation, hydrogenated bisphenol A type epoxide compound (JER (registered trademark) YX8000), alicyclic liquid epoxide compound (Celloxide (registered trademark) 2021P) manufactured by Diacel Corporation, etc. can be used.

[0137] Polyester resin is a polymer containing an ester bond in the repeating unit of the main chain, and can be obtained, for example, by polycondensing a polycarboxylic acid (dicarboxylic acid) and a polyol (diol). Examples of the polyester resin include polyethylene terephthalate, polybutylene terephthalate, polypropylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, etc. For example, the OKP series manufactured by Osaka Gas Chemicals Co., Ltd., the TRN series manufactured by Teijin Limited, TEONEX (registered trademark), Rynite (registered trademark) manufactured by DuPont Company, NOVAPEX (registered trademark) manufactured by Mitsubishi Chemical Corporation, NOVADURAN (registered trademark) manufactured by Mitsubishi Engineering Plastics Corporation, LUMIRROR (registered trademark), TORAYCON (registered trademark) manufactured by Toray Industries, Inc., ELITEL (registered trademark) manufactured by Unitika Ltd., etc. can be used.

[0138] The polyarylate resin is a polymer obtained by polycondensing a diphenol compound and a dicarboxylic acid (such as an aromatic dicarboxylic acid like phthalic acid), and has repeating units containing an aromatic ring and an ester bond in the repeating units of the main chain. As the polyarylate resin, for example, VECTRAN (registered trademark) manufactured by Kuraray Co., Ltd., UPOLYMER (registered trademark), UNIFINER (registered trademark) manufactured by Unitika Ltd., etc. can be used.

[0139] The polyamide resin is a polymer containing an amide bond in the repeating units of the main chain, and can be obtained, for example, by polycondensing a diamine and a dicarboxylic acid. The polyamide resin can be a polyamide resin having an aliphatic skeleton in the main chain. As such an amide resin, for example, nylon can be used. The polyamide resin can also be a polyamide resin having an aromatic skeleton. As such a polyamide resin, aramid resin is known. Considering excellent heat resistance and strong mechanical strength, it is preferable to use aramid resin. For example, Twaron (registered trademark), CONEX (registered trademark) manufactured by Teijin Limited, KEVLAR (registered trademark), NOMEX (registered trademark) manufactured by DuPont Company, etc. can be used.

[0140] The polycarbonate resin is a polymer containing a carbonate group (-O-(C=O)-O-) in the repeating units of the main chain. As the polycarbonate resin, Panlite (registered trademark) manufactured by Teijin Limited, Iupilon (registered trademark), NOVAREX (registered trademark), XANTAR (registered trademark) manufactured by Mitsubishi Engineering Plastics Corporation, SD POLYCA (registered trademark) manufactured by Sumika Styron Polycarbonate Company, etc. can be used.

[0141] The polysulfone resin is a polymer having repeating units containing an aromatic ring, a sulfonyl group (-SO2-), and an oxygen atom. As the polysulfone resin, for example, SUMIKAEXCEL (registered trademark) PES3600P, PES4100P manufactured by Sumitomo Chemical Company, UDEL (registered trademark) P-1700 manufactured by Solvay Specialty Polymers, etc. can be used.

[0142] The fluorinated aromatic polymer is a polymer having repeating units containing an aromatic ring having one or more fluorine atoms and at least one bond selected from the group consisting of an ether bond, a ketone bond, a sulfone bond, an amide bond, an imide bond, and an ester bond. Among them, it is preferably a polymer that must contain the following repeating units, which contain an aromatic ring having one or more fluorine atoms and an ether bond. As the fluorinated aromatic polymer, for example, the fluorinated aromatic polymer described in Japanese Unexamined Patent Application Publication No. 2008-181121 can be used.

[0143] The resin component preferably has high transparency, whereby it is easy to appropriately apply the resin composition to optical uses. For example, the total light transmittance of the resin component at a thickness of 0.1 mm is preferably 75% or more, more preferably 80% or more, and further preferably 85% or more. The upper limit of the total light transmittance of the resin component is not particularly limited, and it may be 100% or less, for example, it may be 95% or less. The total light transmittance is measured based on JIS K 7105.

[0144] The resin component preferably has a high glass transition temperature (Tg), whereby the heat resistance of the resin composition and various molded articles obtained therefrom can be improved. The glass transition temperature of the resin component is, for example, preferably 110°C or higher, more preferably 120°C or higher, and further preferably 130°C or higher. The upper limit of the glass transition temperature of the resin component is not particularly limited, and from the aspect of ensuring the moldability of the resin composition, it is preferably 380°C or lower, for example.

[0145] The resin composition may contain a solvent. For example, in the case where the resin composition is a resin composition that has been made into a coating, the coating of the resin composition becomes easy by containing a solvent. The resin composition containing a solvent can also be used as an ink composition.

[0146] The solvent may be a solvent that functions to dissolve the components contained in the resin composition, or a solvent that functions as a dispersion medium, and is preferably a solvent in which the cyanine compound of the present invention is soluble. As the solvent, a solvent that can be used for the cyanine compound solution described above can be used.

[0147] Regarding the content of the solvent, in 100% by mass of the resin composition, it is, for example, preferably 50% by mass or more, more preferably 70% by mass or more, and in addition, preferably less than 100% by mass, more preferably 95% by mass or less. By adjusting the content of the solvent to such a range, it is easy to obtain a resin composition with a high concentration of cyanine compound.

[0148] The resin composition may contain a surface conditioner, whereby when the resin composition is cured to form a resin layer, the generation of appearance defects such as streaks and depressions on the resin layer can be suppressed. The type of the surface conditioner is not particularly limited, and a silicone surfactant, an acetylenic diol surfactant, a fluorine surfactant, an acrylic leveling agent, etc. can be used. As the surface conditioner, for example, the BYK (registered trademark) series manufactured by BYK-Chemie GmbH, the KF series manufactured by Shin-Etsu Chemical Co., Ltd., etc. can be used.

[0149] The resin composition may contain a dispersant, whereby even if a part of the cyanine compound in the resin composition is present in a dispersed state, the dispersibility is stabilized and re-aggregation of the cyanine compound can be inhibited. There is no particular limitation on the type of the dispersant, and the EFKA series manufactured by EFK Additives, the BYK (registered trademark) series manufactured by BYK-Chemie, the Solsperse (registered trademark) series manufactured by Lubrizol Japan, the DISPARLON (registered trademark) series manufactured by Kusumoto Chemicals, the AJISPER (registered trademark) series manufactured by Ajinomoto Fine-Techno, the KP series manufactured by Shin-Etsu Chemical, the POLYFLOW series manufactured by Kyoeisha Chemical, the MEGAFAC (registered trademark) series manufactured by DIC, the DISPERSANT series manufactured by San Nopco, etc. can be used.

[0150] The resin composition may contain a silane coupling agent, its hydrolysis product or hydrolysis condensate, whereby when the resin composition is cured on a substrate to form a resin layer, the adhesion of the resin layer to the substrate can be improved.

[0151] The resin composition may contain various additives such as a plasticizer, a surfactant, a viscosity modifier, an antifoaming agent, a preservative, a specific resistance modifier, etc. as needed.

[0152] The resin composition can form a cured product by curing. The resin composition can be a resin composition cured by heating (softening) and cooling, a resin composition cured by reaction of resin components (e.g., polymerization reaction, crosslinking reaction), or a resin composition cured by removing the solvent contained in the resin composition. As the resin composition, for example, a thermoplastic resin composition formed by injection molding, extrusion molding, etc. can be used; a resin composition made into a coating that can be applied by a spin coating method, a solvent casting method, a roll coating method, a spraying method, a bar coating method, a dipping method, a screen printing method, a flexographic printing method, an inkjet method, etc.

[0153] In the case where the resin composition is a thermoplastic resin composition, a cured product can be obtained by injection molding, extrusion molding, vacuum molding, compression molding, blow molding, etc. of the resin composition. In this method, a molded product can be obtained by compounding a cyanine compound in a thermoplastic resin and performing heat molding. For example, it is preferable to add a cyanine compound to the powder or granules of the base resin, heat it to about 150°C to 350°C, dissolve it, and then perform molding. The shape of the molded product is not particularly limited, and examples include: plate shape, sheet shape, granular shape, powder shape, block shape, particle aggregate shape, spherical shape, ellipsoidal shape, lens shape, cubic shape, columnar shape, rod shape, cone shape, cylindrical shape, needle shape, fibrous shape, hollow fiber shape, porous shape, etc. In addition, when kneading the resin, additives usually used for resin molding such as plasticizers can be added.

[0154] In the case where the resin composition is a coated resin composition, a cured product in the form of a film with a thickness of 200 μm or less or a sheet with a thickness exceeding 200 μm can be obtained by coating a liquid or paste-like resin composition containing a cyanine compound on a substrate (such as a resin plate, film, glass plate, etc.). The cured product thus obtained can be peeled off from the substrate and processed in the form of a film or sheet, or can be processed integrally with the substrate.

[0155] The cured product of the resin composition can be composed of a single resin layer (a layer formed by curing the resin composition), or can be composed of multiple resin layers. In the case where the cured product is processed integrally with the substrate, the cured product can be formed only on one surface of the substrate, or can be formed on both surfaces. It should be noted that a member formed by integrating the cured product with the substrate can also be formed by thermocompression bonding or chemical bonding of a molded body formed from the resin composition to the substrate.

[0156] The resin composition of the present invention can preferably be used as a resin composition for forming a filter used in various applications such as optical device applications, display device applications, mechanical parts, electrical / electronic components, etc. The resin composition and its cured product can be preferably applied to, for example, filters such as near-infrared cut-off filters. Such a filter can be formed from a single or multiple resin layers, or can be integrally formed with a support.

[0157] A filter integrated with a support can be formed, for example, by spin coating or solvent casting the resin composition on the surface of the support (or, in the case where there is another layer such as an adhesive layer between the support and the resin layer, on the surface of the other layer), and then drying or curing it. In addition, a filter can also be formed by thermocompression bonding a planar molded body formed from the resin composition to the support.

[0158] The resin layer formed from the resin composition may be provided only on one side of the support, or may be provided on both sides. The thickness of the resin layer is not particularly limited, and from the viewpoint of ensuring the desired near-infrared cut-off performance, for example, it is preferably 0.5 μm or more, more preferably 1 μm or more, further preferably 2 μm or more, and in addition, it is preferably 1 mm or less, more preferably 500 μm or less, further preferably 200 μm or less. When the resin layer is formed by an operation such as coating the resin composition that has been made into a coating solution on the support, the strength of the filter can be ensured by the support, so the thickness of the resin layer can be further reduced. When the resin layer is formed on the support, the thickness of the resin layer is, for example, preferably 50 μm or less, more preferably 20 μm or less, further preferably 10 μm or less, and particularly preferably 5 μm or less.

[0159] As the support, it is preferable to use a transparent substrate such as a resin plate, a resin film, or a glass plate. For the resin plate or resin film used as the support, for example, it is preferable to use the resin plate or resin film formed from the resin components described above. From the viewpoint of improving the heat resistance of the optical filter, it is preferable to use a glass substrate as the support, and the optical filter formed in this way can be mounted on an electronic component by reflow soldering, for example. In addition, the glass substrate is not easily broken or warped even when exposed to high temperatures, so it is easy to ensure the adhesion to the resin layer. When using a glass substrate as the support, an adhesive layer formed of a silane coupling agent, for example, can be provided between the support and the resin layer, whereby the adhesion between the resin layer and the glass substrate can be improved. It should be noted that even if a silane coupling agent is contained in the resin composition for forming the resin layer as an adhesion improver, the adhesion between the resin layer and the glass substrate can be improved.

[0160] The thickness of the support (substrate) is, for example, preferably 0.05 mm or more, more preferably 0.1 mm or more, from the viewpoint of ensuring strength, and in addition, from the viewpoint of thinning, it is preferably 0.4 mm or less, more preferably 0.3 mm or less.

[0161] A protective layer made of the same or different resin as the resin layer can be laminated on the resin layer formed from the resin composition as the second resin layer. By providing the protective layer, the durability (decomposition resistance) of the cyanine compound contained in the resin layer can be improved. The protective layer may be provided only on one side of the resin layer, or may be provided on both sides. When the resin layer is provided on the support, the protective layer is preferably provided on the surface of the resin layer opposite to the support.

[0162] When a filter is formed from the resin composition of the present invention, the filter may have an antireflective and antiglare layer (antireflection film) that reduces the ingress of light from a fluorescent lamp or the like, a layer having antiscratch performance, a transparent substrate having other functions, and the like. The filter may have a near-infrared reflection film and an ultraviolet reflection film. These antireflection films, reflection films, or other layers are preferably provided closer to the light-incident side than the resin layer.

[0163] The near-infrared reflection film, the ultraviolet reflection film, and the antireflection film (visible light antireflection film) may be composed of a dielectric film. The dielectric film is usually configured as a dielectric multilayer film formed by alternately laminating a high-refractive-index material layer and a low-refractive-index material layer, but it may also be composed of only one of the high-refractive-index material layer and the low-refractive-index material layer. As the material for forming the high-refractive-index material layer, a material having a refractive index of 1.7 or more can be used, preferably a material having a refractive index range of 1.7 or more and 2.5 or less, more preferably the refractive index range is 1.8 or more, and further preferably 2.0 or more. Examples of the material for forming the high-refractive-index material layer include oxides such as titanium oxide, zinc oxide, zirconium oxide, lanthanum oxide, yttrium oxide, indium oxide, niobium oxide, tantalum oxide, tin oxide, and bismuth oxide; nitrides such as silicon nitride; mixtures of the oxides and the nitrides, materials containing doped metals such as aluminum and copper and carbon therein (e.g., indium tin oxide (ITO) doped with tin, antimony-doped tin oxide (ATO)), and the like. As the material for forming the low-refractive-index material layer, a material having a refractive index less than 1.7 can be used, preferably a material having a refractive index range of 1.2 to 1.6, and more preferably a refractive index range of 1.3 to 1.5. Examples of the material for forming the low-refractive-index material layer include silicon oxide (silicon dioxide, SiOx (x = 1 to 2)), aluminum oxide, lanthanum fluoride, magnesium fluoride, and sodium hexafluoroaluminate. Among them, the high-refractive-index material layer is preferably composed of titanium oxide, and the low-refractive-index material layer is preferably composed of silicon oxide.

[0164] The thicknesses of the high-refractive-index material layer and the low-refractive-index material layer are preferably adjusted to a range of 0.1λ to 0.5λ of the wavelength λ (nm) of the light to be blocked, and more preferably adjusted to a range of 0.2λ to 0.3λ. By forming the dielectric film in this way, light in a desired wavelength region can be selectively reflected, and a near-infrared reflection film, an ultraviolet reflection film, an antireflection film (visible light antireflection film), etc. can be formed from the dielectric film. The ultraviolet reflection film and the near-infrared reflection film may also be a film having both ultraviolet reflection function and near-infrared reflection function.

[0165] The number of dielectric films is not particularly limited as long as it is one or more, but from the viewpoint of exhibiting desired optical properties such as a near-infrared reflection film, an ultraviolet reflection film, an antireflection film, etc., it is preferably 2 to 80 layers, for example. The number of dielectric films can be 5 or more, 10 or more, or 20 or more, and can also be 70 or less or 60 or less. The thickness of the dielectric film is not particularly limited, and for example, it can be in the range of 0.01 μm to 10 μm, but from the viewpoint of sufficiently blocking the incidence of light in the desired wavelength region, it is preferably 0.02 μm or more, more preferably 0.03 μm or more. In addition, from the viewpoint of thinning, it is preferably 5 μm or less, more preferably 3 μm or less.

[0166] The optical filter can have an aluminum vapor deposition film, a noble metal thin film, a resin film in which metal oxide fine particles mainly composed of indium oxide and containing a small amount of tin oxide are dispersed, etc.

[0167] The thickness of the optical filter is preferably 1 mm or less, for example. Thereby, for example, the requirements for miniaturization of the imaging element can be sufficiently met. The thickness of the optical filter is more preferably 500 μm or less, further preferably 300 μm or less, further more preferably 150 μm or less, and is preferably 30 μm or more, more preferably 50 μm or more.

[0168] The optical filter can be used as one of the constituent components of sensors such as an image sensor (imaging element), an illuminance sensor, a proximity sensor, etc. For example, an image sensor is used as an electronic component that converts the light of a subject into an electrical signal and outputs it, and examples include: CCD (Charge Coupled Device), CMOS (Complementary Metal - Oxide Semiconductor), etc. The image sensor can be used for cameras for mobile phones, digital cameras, in - vehicle cameras, surveillance cameras, display elements (LEDs, etc.). The sensor includes one or two or more of the above - mentioned optical filters, and can further have other optical filters (such as a visible - light cut - off filter, an infrared - cut - off filter, an ultraviolet - cut - off filter, etc.), lenses as needed.

[0169] This application claims the benefit of priority based on Japanese Patent Application No. 2022 - 199687 filed on December 14, 2022. The entire contents of the specification of Japanese Patent Application No. 2022 - 199687 filed on December 14, 2022 are incorporated herein by reference.

[0170] Examples

[0171] Hereinafter, examples are listed to more specifically illustrate the present invention. However, the present invention is not limited by the following examples, and can also be appropriately modified and implemented within the scope that can conform to the gist of the preceding and following texts, and these are all included in the technical scope of the present invention.

[0172] (1) Synthesis of Compounds (1-1) Synthesis Example 1: Synthesis of Diphenylamine Salt 1

[0173] According to the method described in Bioconjugate Chemistry, 29(11), p.3886-3895 (2018), N-((1E)-2-phenyl-3-((E)-(phenylimino)methyl)cyclohex-2-en-1-ylidene)methyl)aniline hydrochloride (diphenylamine salt 1) shown in Table 1 was synthesized.

[0174] (1-2) Synthesis Example 2: Synthesis of Diphenylamine Salt 2

[0175] According to the method described in paragraph 0100 of International Publication No. 2012 / 026316, N-((1E)-2-chloro-3-((E)-(phenylimino)methyl)cyclohex-2-en-1-ylidene)methyl)aniline hydrochloride (diphenylamine salt 2) shown in Table 1 was synthesized.

[0176] (1-3) Synthesis Example 3: Synthesis of Diphenylamine Salt 3

[0177] According to the method described in paragraph 0100 of International Publication No. 2012 / 026316, N-((1E)-2-chloro-3-((E)-(phenylimino)methyl)cyclopent-2-en-1-ylidene)methyl)aniline hydrochloride (diphenylamine salt 3) shown in Table 1 was synthesized.

[0178] (1-4) Synthesis Example 4: Synthesis of Diphenylamine Salt 4

[0179] According to the method described in paragraph 0197 of International Publication No. 2021 / 085372, N-((1E)-2-diphenylamino-3-((E)-(phenylimino)methyl)cyclopent-2-en-1-ylidene)methyl)aniline tetrafluoroborate (diphenylamine salt 4) shown in Table 1 was synthesized.

[0180] (1-5) Synthesis Example 5: Synthesis of Diphenylamine Salt 5

[0181] According to the method described in paragraph 0052 of Japanese Patent Application Laid-Open No. 2005-336236, N-((1E,3E,5E,7E)-7-(phenylimino)hepta-1,3,5-triene-1-yl)aniline hydrochloride (diphenylamine salt 5) shown in Table 1 was synthesized.

[0182] [Table 1]

[0183]

[0184] (1-6) Synthesis Example 6: Synthesis of Acetyl Compound 1

[0185] In a 500 mL four-necked flask placed in a water bath, under a nitrogen flow (10 mL / min), while paying attention to heat generation, 21.9 g (0.195 mol) of potassium tert-butoxide, 98.1 g of super-dehydrated tetrahydrofuran, 10.8 g (0.065 mol) of fluorene, and 11.5 g (0.13 mol) of ethyl acetate were successively added. Then, while heating in the water bath, the mixture was stirred under reflux conditions for 3 hours. After cooling the resulting reaction solution, it was quenched with dilute hydrochloric acid, then extracted with ethyl acetate, and washed 3 times with brine. The obtained organic phase was dehydrated with magnesium sulfate, concentrated using an evaporator, and then the resulting solid was purified by silica gel column chromatography (developing solvent: ethyl acetate) to obtain 12.5 g of 9-acetyl-9H-fluorene (acetyl compound 1). The yield relative to fluorene was 92.4 mol%.

[0186] (1-7) Synthesis Example 7: Synthesis of Acetyl Compound 2

[0187] In Synthesis Example 6, 2,7-di-tert-butylfluorene was used instead of fluorene, and otherwise, the same operations as in Synthesis Example 6 were carried out to obtain 5.84 g of 2,7-di-tert-butyl-9-acetyl-9H-fluorene (acetyl compound 2). The yield relative to 2,7-di-tert-butylfluorene was 98.0 mol%.

[0188] (1-8) Synthesis Example 8: Synthesis of Acetyl Compound 3

[0189] In Synthesis Example 6, indene was used instead of fluorene, and otherwise, the same operations as in Synthesis Example 6 were carried out to obtain 3.08 g of 1-(1H-inden-1-yl)ethan-1-one (acetyl compound 3). The yield relative to indene was 45.3 mol%.

[0190] (1-9) Synthesis Example 9: Synthesis of Comparative Cyanine Compound 1

[0191] In a 500 mL separable flask, 6.2 g (0.026 mol) of the acetyl compound 1 obtained in Synthesis Example 6 (the acetyl compound of formula (8)), 5.0 g (0.026 mol) of 1-naphthylhydrazine hydrochloride (the hydrazine hydrochloride of formula (7)), and 112.1 g of tert-amyl alcohol as a solvent were charged. While stirring under a nitrogen flow (10 mL / min), the reaction was carried out at 90 °C for 4 hours. After the reaction was completed, the reaction solution was cooled to room temperature, quenched with 100 g of water, and extracted with 100 g of ethyl acetate. The obtained organic phase was dehydrated with magnesium sulfate, concentrated by an evaporator, and then the obtained solid was purified by silica gel column chromatography (developing solvent: chloroform) to obtain 4.4 g of indolenine compound 1 (the compound of formula (5)). The yield relative to the acetyl compound 1 was 51.3 mol%.

[0192] Next, in a 100 mL four-necked flask, 2.2 g (0.007 mol) of the above-obtained indolenine compound 1, 11.2 g (0.079 mol) of methyl iodide, and 53.3 g of N,N-dimethylformamide were charged. While stirring under a nitrogen flow (5 mL / min), the reaction was carried out at 80 °C for 6 hours. After cooling to room temperature, the reaction solution was precipitated in 300 g of toluene, and the precipitated solid was filtered to obtain 1.8 g of indolium salt (the nitrogen-containing heterocyclic compound of formula (4)). The yield relative to the indolenine compound 1 was 56.5 mol%.

[0193] [Chemical formula 12]

[0194]

[0195] In a 100 mL four-necked flask, 1.0 g (0.0021 mol) of the above-obtained indolium salt, 0.42 g (0.0011 mol) of diphenylamine salt 1 obtained in Synthesis Example 1, 0.28 g (0.003 mol) of sodium acetate, 9.9 g of acetic acid, and 10.1 g of acetic anhydride were added. The reaction was carried out by stirring at 100 °C for 8 hours. The reaction solution was cooled to room temperature, 150 g of water was added thereto, and the precipitated solid was filtered. The solid was purified by silica gel column chromatography (developing solvent: chloroform) to obtain 0.21 g of Comparative cyanine compound 1 shown in Table 4. The yield relative to the indolium salt was 10.1 mol%.

[0196] [Chemical formula 13]

[0197]

[0198] (1-10) Synthesis Example 10: Synthesis of cyanine compound 1

[0199] Dissolve 0.50 g (0.50 mmol) of the comparative cyanine compound 1 obtained in Synthesis Example 9 in 20 mL of acetone, add 6.7 g (0.10 mmol) of a 10.5% aqueous solution of sodium tetrakis(pentafluorophenyl)borate (manufactured by Nippon Shokubai Co., Ltd.), and stir overnight at room temperature. After concentrating the reaction solution with an evaporator, it was purified by silica gel column chromatography (developing solvent: chloroform) to obtain 0.57 g of the cyanine compound 1 shown in Table 2. The yield relative to the comparative cyanine compound 1 was 74.3 mol%. It should be noted that the pKa of the tetrakis(pentafluorophenyl)borate anion of the cyanine compound 1 is -8.0 or less.

[0200] [Chemical formula 14]

[0201]

[0202] (1 - 11) Synthesis Example 11: Synthesis of cyanine compound 2

[0203] In Synthesis Example 9, 1-phenylhydrazine hydrochloride was used instead of 1-naphthylhydrazine hydrochloride, and acetyl compound 2 was used instead of acetyl compound 1. Otherwise, the cyanine compound 2 shown in Table 2 was obtained by the same operations as in Synthesis Examples 9 and 10. The yield relative to the indolium salt was 11.1 mol%.

[0204] (1 - 12) Synthesis Example 12: Synthesis of cyanine compound 3

[0205] In Synthesis Example 9, 1-phenylhydrazine hydrochloride was used instead of 1-naphthylhydrazine hydrochloride. Otherwise, the cyanine compound 3 shown in Table 2 was obtained by the same operations as in Synthesis Examples 9 and 10. The yield relative to the indolium salt was 9.9 mol%.

[0206] (1 - 13) Synthesis Example 13: Synthesis of cyanine compound 4

[0207] In Synthesis Example 9, 1-phenylhydrazine hydrochloride was used instead of 1-naphthylhydrazine hydrochloride, and acetyl compound 3 was used instead of acetyl compound 1. Otherwise, the cyanine compound 4 shown in Table 2 was obtained by the same operations as in Synthesis Examples 9 and 10. The yield relative to the indolium salt was 3.6 mol%.

[0208] (1 - 14) Synthesis Example 14: Synthesis of comparative cyanine compound 2

[0209] In Synthesis Example 9, 2,3,3-trimethylpseudindole (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of pseudindole compound 1, and acetonitrile was used instead of N,N-dimethylformamide as the solvent. Otherwise, the comparative cyanine compound 2 shown in Table 4 was obtained by the same operations as in Synthesis Example 9. The yield relative to the indolium salt was 21.3 mol%.

[0210] (1-15) Synthesis Example 15: Synthesis of Comparative Cyanine Compound 3

[0211] In Synthesis Example 9, 1-phenylhydrazine hydrochloride was used instead of 1-naphthylhydrazine hydrochloride, and diphenylamine salt 2 was used instead of diphenylamine salt 1. Otherwise, Comparative Cyanine Compound 3 shown in Table 4 was obtained by the same operation as in Synthesis Example 9. The yield relative to the indolium salt was 40.7 mol%.

[0212] (1-16) Synthesis Example 16: Synthesis of Cyanine Compound 5

[0213] Using Comparative Cyanine Compound 3 obtained in Synthesis Example 15, Cyanine Compound 5 shown in Table 2 was obtained by the same operation as in Synthesis Example 10. The yield relative to Comparative Cyanine Compound 3 was 89.9 mol%.

[0214] (1-17) Synthesis Example 17: Synthesis of Cyanine Compound 6

[0215] Using Comparative Cyanine Compound 3 obtained in Synthesis Example 15 and phenol, Cyanine Compound 6 shown in Table 2 was obtained by the method described in J. Phys. Chem. A, 118, 4038 - 4047 (2014) and the same operation as in Synthesis Example 10. The yield relative to Comparative Cyanine Compound 3 was 18.2 mol%.

[0216] (1-18) Synthesis Example 18: Synthesis of Cyanine Compound 7

[0217] Using Comparative Cyanine Compound 3 obtained in Synthesis Example 15 and acetyl chloride, Cyanine Compound 7 shown in Table 2 was obtained by the method described in Chem. Eur. J., 22, 12282 - 12285 (2016) and the same operation as in Synthesis Example 10. The yield relative to Comparative Cyanine Compound 3 was 43.1 mol%.

[0218] (1-19) Synthesis Example 19: Synthesis of Cyanine Compound 8

[0219] In Synthesis Example 9, diphenylamine salt 3 was used instead of diphenylamine salt 1. Otherwise, Cyanine Compound 8 shown in Table 2 was obtained by the same operation as in Synthesis Examples 9 and 10. The yield relative to the indolium salt was 8.0 mol%.

[0220] (1-20) Synthesis Example 20: Synthesis of Comparative Cyanine Compound 4

[0221] In Synthesis Example 9, 1-phenylhydrazine hydrochloride was used instead of 1-naphthylhydrazine hydrochloride, and diphenylamine salt 3 was used instead of diphenylamine salt 1. Otherwise, Comparative Cyanine Compound 4 shown in Table 4 was obtained by the same operation as in Synthesis Example 9. The yield relative to the indolium salt was 48.3 mol%.

[0222] (1-21) Synthesis Example 21: Synthesis of Cyanine Compound 9

[0223] Using the comparative cyanine compound 4 obtained in Synthesis Example 20, cyanine compound 9 shown in Table 2 was obtained by the same operation as in Synthesis Example 10. The yield relative to the comparative cyanine compound 4 was 91.4 mol%.

[0224] (1-22) Synthesis Example 22: Synthesis of Cyanine Compound 10

[0225] In Synthesis Example 9, diphenylamine salt 3 was used instead of diphenylamine salt 1, and otherwise, the iodide salt of cyanine compound 10 shown in Table 2 was obtained by the same operation as in Synthesis Example 9. Subsequently, cyanine compound 10 was obtained by the method described in paragraph 0220 of International Publication No. 2014 / 057032 and the same operation as in Synthesis Example 10. The yield relative to the indolium salt was 60.0 mol%.

[0226] (1-23) Synthesis Example 23: Synthesis of Cyanine Compound 11

[0227] Using the comparative cyanine compound 4 obtained in Synthesis Example 20, cyanine compound 11 shown in Table 3 was obtained by the method described in paragraph 0220 of International Publication No. 2014 / 057032 and the same operation as in Synthesis Example 10. The yield relative to the comparative cyanine compound 4 was 89.7 mol%. (1-24) Synthesis Example 24: Synthesis of Cyanine Compound 12

[0228] In Synthesis Example 9, 1-phenylhydrazine hydrochloride was used instead of 1-naphthylhydrazine hydrochloride, and diphenylamine salt 4 was used instead of diphenylamine salt 1, and otherwise, cyanine compound 12 shown in Table 3 was obtained by the same operation as in Synthesis Examples 9 and 10. The yield relative to the indolium salt was 33.6 mol%.

[0229] (1-25) Synthesis Example 25: Synthesis of Comparative Cyanine Compound 5

[0230] In Synthesis Example 9, 1-phenylhydrazine hydrochloride was used instead of 1-naphthylhydrazine hydrochloride, and malondialdehyde diphenylamine hydrochloride (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of diphenylamine salt 1, and otherwise, comparative cyanine compound 5 shown in Table 4 was obtained by the same operation as in Synthesis Example 9. The yield relative to the indolium salt was 20.1 mol%.

[0231] (1-26) Synthesis Example 26: Synthesis of Cyanine Compound 13

[0232] Using the comparative cyanine compound 5 obtained in Synthesis Example 25, cyanine compound 13 shown in Table 3 was obtained by the same operation as in Synthesis Example 10. The yield relative to the comparative cyanine compound 5 was 89.8 mol%.

[0233] (1-27) Synthesis Example 27: Synthesis of Comparative Cyanine Compound 6

[0234] In Synthesis Example 25, 4-fluorophenylhydrazine hydrochloride was used instead of 1-phenylhydrazine hydrochloride, and otherwise, the same operations as in Synthesis Example 25 were carried out to obtain Comparative Cyanine Compound 6 shown in Table 4. The yield relative to the indolium salt was 49.7 mol%.

[0235] (1-28) Synthesis Example 28: Synthesis of Cyanine Compound 14

[0236] Using Comparative Cyanine Compound 6 obtained in Synthesis Example 27, Cyanine Compound 14 shown in Table 3 was obtained by the same operations as in Synthesis Example 10. The yield relative to Comparative Cyanine Compound 6 was 86.4 mol%.

[0237] (1-29) Synthesis Example 29: Synthesis of Comparative Cyanine Compound 7

[0238] In Synthesis Example 25, 4-chlorophenylhydrazine hydrochloride was used instead of 1-phenylhydrazine hydrochloride, and otherwise, the same operations as in Synthesis Example 25 were carried out to obtain Comparative Cyanine Compound 7 shown in Table 4. The yield relative to the indolium salt was 53.4 mol%.

[0239] (1-30) Synthesis Example 30: Synthesis of Cyanine Compound 15

[0240] Using Comparative Cyanine Compound 7 obtained in Synthesis Example 29, Cyanine Compound 15 shown in Table 3 was obtained by the same operations as in Synthesis Example 10. The yield relative to Comparative Cyanine Compound 7 was 90.1 mol%.

[0241] (1-31) Synthesis Example 31: Synthesis of Comparative Cyanine Compound 8

[0242] In Synthesis Example 25, 4-bromophenylhydrazine hydrochloride was used instead of 1-phenylhydrazine hydrochloride, and otherwise, the same operations as in Synthesis Example 25 were carried out to obtain Comparative Cyanine Compound 8 shown in Table 4. The yield relative to the indolium salt was 42.6 mol%.

[0243] (1-32) Synthesis Example 32: Synthesis of Cyanine Compound 16

[0244] Using Comparative Cyanine Compound 8 obtained in Synthesis Example 31, Cyanine Compound 16 shown in Table 3 was obtained by the same operations as in Synthesis Example 10. The yield relative to Comparative Cyanine Compound 8 was 88.8 mol%.

[0245] (1-33) Synthesis Example 33: Synthesis of Comparative Cyanine Compound 9

[0246] In Synthesis Example 25, 4-methylphenylhydrazine hydrochloride was used instead of 1-phenylhydrazine hydrochloride, and the same procedure as in Synthesis Example 25 was carried out to obtain Comparative Cyanine Compound 9 shown in Table 4. The yield relative to the indolium salt was 65.8 mol%.

[0247] (1-34) Synthesis Example 34: Synthesis of Cyanine Compound 17

[0248] Using Comparative Cyanine Compound 9 obtained in Synthesis Example 33, Cyanine Compound 17 shown in Table 3 was obtained by the same procedure as in Synthesis Example 10. The yield relative to Comparative Cyanine Compound 9 was 89.6 mol%.

[0249] (1-35) Synthesis Example 35: Synthesis of Comparative Cyanine Compound 10

[0250] In Synthesis Example 25, 4-methoxyphenylhydrazine hydrochloride was used instead of 1-phenylhydrazine hydrochloride, and the same procedure as in Synthesis Example 25 was carried out to obtain Comparative Cyanine Compound 10 shown in Table 4. The yield relative to the indolium salt was 17.8 mol%.

[0251] (1-36) Synthesis Example 36: Synthesis of Cyanine Compound 18

[0252] Using Comparative Cyanine Compound 10 obtained in Synthesis Example 35, Cyanine Compound 18 shown in Table 3 was obtained by the same procedure as in Synthesis Example 10. The yield relative to Comparative Cyanine Compound 10 was 87.5 mol%.

[0253] (1-37) Synthesis Example 37: Synthesis of Comparative Cyanine Compound 11

[0254] In Synthesis Example 25, 4-(trifluoromethyl)phenylhydrazine hydrochloride was used instead of 1-phenylhydrazine hydrochloride, and the same procedure as in Synthesis Example 25 was carried out to obtain Comparative Cyanine Compound 11 shown in Table 4. The yield relative to the indolium salt was 67.6 mol%.

[0255] (1-38) Synthesis Example 38: Synthesis of Cyanine Compound 19

[0256] Using Comparative Cyanine Compound 11 obtained in Synthesis Example 37, Cyanine Compound 19 shown in Table 3 was obtained by the same procedure as in Synthesis Example 10. The yield relative to Comparative Cyanine Compound 11 was 88.2 mol%.

[0257] (1-39) Synthesis Example 39: Synthesis of Cyanine Compound 20

[0258] In Synthesis Example 9, 1-phenylhydrazine hydrochloride was used instead of 1-naphthylhydrazine hydrochloride, and diphenylamine salt 5 (manufactured by Tokyo Chemical Industry Co., Ltd.) was used instead of diphenylamine salt 1. Otherwise, the cyanine compound 20 shown in Table 3 was obtained by the same operations as in Synthesis Examples 9 and 10. The yield relative to the indolium salt was 18.4 mol%.

[0259] (1-40) Synthesis Example 40: Synthesis of cyanine compound 21

[0260] In Synthesis Example 9, 1-phenylhydrazine hydrochloride was used instead of 1-naphthylhydrazine hydrochloride, and diphenylamine salt 5 was used instead of diphenylamine salt 1. Otherwise, the cyanine compound 21 shown in Table 4 was obtained by the same operations as in Synthesis Examples 9 and 10. The yield relative to the indolium salt was 5.9 mol%.

[0261] [Table 2]

[0262]

[0263] [Table 3]

[0264]

[0265] [Table 4]

[0266]

[0267] (2) Preparation of cyanine compound solution (2-1) Solubility

[0268] A specified amount of the cyanine compounds 1 to 21 and comparative cyanine compounds 1 to 11 shown in Tables 2 to 4 was added to toluene in a 10 mL glass sample bottle and stirred at 25°C. The cyanine compound was added to toluene to make the concentration 0.1 mass% or 1.0 mass%, and the resulting solution was visually checked for insolubles (turbidity). The evaluation when insolubles were found at a concentration of 0.1 mass% was set as C, the evaluation when insolubles were not found at a concentration of 0.1 mass% but were found at a concentration of 1.0 mass% was set as B, and the evaluation when insolubles were not found at a concentration of 1.0 mass% was set as A. The results are shown in Table 5. The cyanine compounds 1 to 21 showed high solubility in toluene.

[0269] (2-2) Spectrophotometric measurement

[0270] Prepare methanolic solutions of cyanine compounds 1 to 21 and comparative cyanine compounds 1 to 11, and measure the absorption spectra at wavelengths from 300 nm to 1100 nm. Adjust the concentration of the toluene solution of the cyanine compound so that the transmittance at the maximum absorption wavelength is 10% (±0.05%). Using a spectrophotometer (manufactured by Shimadzu Corporation, UV-1800), measure the transmittance at an interval of 1 nm, and determine the wavelength with the maximum absorption (maximum absorption wavelength λmax) in the wavelength range from 300 nm to 1100 nm. The results are shown in Table 5.

[0271] For ring A 1 and ring A 2 For ring B 1 and ring B 2 Study the influence on the maximum absorption wavelength λmax. Compare the maximum absorption wavelengths λmax of cyanine compounds 1 to 4 and comparative cyanine compound 2. The maximum absorption wavelength λmax of comparative cyanine compound 2 without ring B 1 and ring B 2 is 754 nm. In contrast, relative to comparative cyanine compound 2, the maximum absorption wavelengths λmax of cyanine compounds 2 to 4 bonded with ring B 1 and ring B 2 are 781 to 788 nm, and the maximum absorption wavelength λmax is redshifted by about 30 nm compared to comparative cyanine compound 2. Relative to cyanine compounds 2 to 4, the maximum absorption wavelength λmax of cyanine compound 1 with an extended π-electron system of ring A 1 and ring A 2 is further redshifted to 839 nm.

[0272] According to the comparison between cyanine compound 1 and comparative cyanine compound 1, cyanine compound 5 and comparative cyanine compound 3, cyanine compound 9 and comparative cyanine compound 4, and cyanine compounds 13 to 19 and comparative cyanine compounds 5 to 11, the difference in the anions of the cyanine compounds has almost no influence on the maximum absorption wavelength λmax. The more carbon atoms in the methylene chain, the more the maximum absorption wavelength λmax shows a tendency to be redshifted, and the maximum absorption wavelength λmax also varies depending on the substituents on the methylene chain. The maximum value of the maximum absorption wavelength λmax is 942 nm.

[0273] [Table 5]

[0274] Cyanine compound Toluene solubility λmax Cyanine compound Toluene solubility λmax Cyanine compound 1 A 839 nm Cyanine compound 17 A 674 nm Cyanine compound 2 A 788 nm Cyanine compound 18 A 691 nm Cyanine compound 3 A 788 nm Cyanine compound 19 A 658 nm Cyanine compound 4 A 781 nm Cyanine compound 20 A 755 nm Cyanine compound 5 A 793 nm Cyanine compound 21 A 870 nm Cyanine compound 6 A 781 nm Comparative cyanine compound 1 C 842 nm Cyanine compound 7 A 810 nm Comparative cyanine compound 2 B 754 nm Cyanine compound 8 A 872 nm Comparative cyanine compound 3 C 794 nm Cyanine compound 9 A 818 nm Comparative cyanine compound 4 C 818 nm Cyanine compound 10 A 942 nm Comparative cyanine compound 5 C 663 nm Cyanine compound 11 A 893 nm Comparative cyanine compound 6 C 664 nm Cyanine compound 12 A 833 nm Comparative cyanine compound 7 C 670 nm Cyanine compound 13 A 663 nm Comparative cyanine compound 8 C 672 nm Cyanine compound 14 A 664 nm Comparative cyanine compound 9 C 674 nm Cyanine compound 15 A 670 nm Comparative cyanine compound 10 C 691 nm Cyanine compound 16 A 672 nm Comparative cyanine compound 11 C 658 nm

[0275] (3) Fabrication of the resin laminated substrate (3-1) Synthesis of polyarylate resin

[0276] In a 2 L reaction vessel equipped with a stirring blade, 10.0 g (0.044 mol) of 2,2'-bis(4-hydroxyphenyl)propane, 3.6 g (0.090 mol) of sodium hydroxide, and 300 g of ion-exchanged water were charged and dissolved. After that, 0.89 g (0.009 mol) of triethylamine was added thereto and dissolved. A solution prepared by dissolving 3.6 g (0.021 mol) of terephthaloyl chloride and 3.6 g (0.021 mol) of isophthaloyl chloride in 500 g of dichloromethane was placed in a dropping funnel and installed on the reaction vessel. While maintaining the solution in the reaction vessel at 20 °C and stirring, the dichloromethane solution was added dropwise from the dropping funnel over 60 minutes. Then, a solution prepared by dissolving 0.71 g (0.005 mol) of benzoyl chloride in 10 g of dichloromethane was added thereto and stirred for 60 minutes. An aqueous acetic acid solution was added to the resulting reaction solution for neutralization. After adjusting the pH of the aqueous phase to 7, the oil phase and the aqueous phase were separated using a separatory funnel. The obtained oil phase was added dropwise to methanol with stirring to reprecipitate the polymer, and the precipitate was recovered by filtration and dried in an oven at 80 °C to obtain a white solid polyarylate resin. The yield was 11.5 g. The weight-average molecular weight (Mw) of the obtained polyarylate resin was 33,780, and the number-average molecular weight (Mn) was 8,130. The weight-average molecular weight and the number-average molecular weight of the polyarylate resin were values in terms of polystyrene determined by gel permeation chromatography.

[0277] (3-2) Production Example 1: Production of Resin-Laminated Substrate 1

[0278] 2 parts by mass of the polyarylate resin and 0.1 part by mass of the cyanine compound 1 were added to 38 parts by mass of toluene and uniformly mixed at room temperature to obtain Resin Composition 1. After dropping 2 cc of Resin Composition 1 onto a glass substrate (D263Teco manufactured by Schott), Resin Composition 1 was formed into a film on the glass substrate using a spin coater (1H-D7 manufactured by MIKASA). The glass substrate having Resin Composition 1 formed thereon was initially dried (before curing) at 100 °C for 3 minutes, and then dried in a nitrogen atmosphere at 190 °C for 1 hour using an inert oven (DN610I manufactured by YAMAT Scientific) to obtain Resin-Laminated Substrate 1 (after curing) having a resin layer formed on the glass substrate. The thickness of the resin layer formed on the glass substrate was about 2 μm. It should be noted that the thickness of the resin layer was obtained by measuring the thickness of the glass substrate having the resin layer formed thereon and the thickness of the glass substrate alone with a micrometer, respectively, and calculating the difference between the two.

[0279] (3-3) Production Example 2: Production of Resin-Laminated Substrate 2

[0280] In Production Example 1, cyanine compound 3 was used instead of cyanine compound 1, and otherwise, the operation was the same as in Production Example 1 to produce a resin laminated substrate 2.

[0281] (3-4) Production Example 3: Production of Comparative Resin Laminated Substrate 1

[0282] In Production Example 1, comparative cyanine compound 1 was used instead of cyanine compound 1, and otherwise, the operation was the same as in Production Example 1 to produce a comparative resin laminated substrate 1.

[0283] (3-5) Production Example 4: Production of Comparative Resin Laminated Substrate 2

[0284] In Production Example 1, comparative cyanine compound 2 was used instead of cyanine compound 1, and otherwise, the operation was the same as in Production Example 1 to produce a comparative resin laminated substrate 2.

[0285] (3-6) Spectrophotometric Measurement

[0286] For each resin laminated substrate, a spectrophotometer (manufactured by Shimadzu Corporation, UV-1800) was used to measure the transmission spectrum at a measurement interval of 1 nm, and the transmittance at wavelengths from 300 nm to 1100 nm was determined. The transmission spectra of the resin laminated substrate before and after curing were measured. The measurement results of the transmission spectra of resin laminated substrate 1 and comparative resin laminated substrate 1 are shown in Figure 1 and Figure 2 . In addition, for each resin laminated substrate for which the transmission spectrum was measured, the difference in transmittance before curing and after curing at the maximum absorption wavelength (λmax) (change in transmittance before and after curing) was determined, and thus the heat resistance of the resin was evaluated. The results are shown in Table 6.

[0287] Each resin laminated substrate showed an absorption peak derived from the cyanine compound contained in the resin layer. In resin laminated substrates 1 and 2 and comparative resin laminated substrate 2 using a pentafluorophenylborate anion having a pKa of the conjugate acid of -8.0 or less as a counter anion, almost no change in transmittance before and after curing at the maximum absorption wavelength was observed, indicating excellent heat resistance. On the other hand, in comparative resin laminated substrate 1 using an iodide ion having a pKa of the conjugate acid greater than -8.0 as a counter anion, as shown in Figure 2 , the absorption peak derived from the cyanine compound in the near-infrared region disappeared after curing. It is considered that in comparative resin laminated substrate 1, the cyanine compound decomposed by heating at 190 °C. It should be noted that, as shown in Figure 1 , in resin laminated substrate 1, in the transmission spectrum after curing, a new absorption peak having a maximum absorption at around 1030 nm, which was not observed in cyanine compound 1 in solution, was observed.

[0288] [Table 6]

[0289] Cyanine compound λmax Transmittance change before and after curing Resin laminated substrate 1 Cyanine compound 1 859 nm 3.0％ Resin laminated substrate 2 Cyanine compound 3 803 nm 1.4％ Comparative resin laminated substrate 1 Comparative cyanine compound 1 857 nm 43.0％ Comparative resin laminated substrate 2 Comparative cyanine compound 2 774 nm 0.1％

[0290] Industrial Applicability

[0291] The cyanine compounds of the present invention can be applied, for example, to filters for semiconductor light receiving elements having a function of absorbing / cutting off near-infrared rays, near-infrared absorption films for blocking heat rays for energy saving, near-infrared absorption plates, information display materials such as anti-counterfeiting ink liquids and invisible bar ink liquids, materials for solar cells using visible light and near-infrared light, plasma display panels (PDPs), specific wavelength absorption filters for CCDs, photothermal conversion materials for laser welding, materials for photofixing methods using light that is not easily damaged by pressurization or heating (electrostatic developing toners for flash photofixing methods), cosmetic materials having a function of absorbing or cutting off near-infrared rays, materials for light detection and ranging (LIDAR) systems, etc. The filters and specific wavelength absorption filters can be used for cameras for mobile phones, digital cameras, in-vehicle cameras, surveillance cameras, display elements (LEDs, etc.).

Claims

1. A cyanine compound, characterized in that, represented by the following formula (1): [Chemical formula 1] In formula (1), Ring A 1 and Ring A 2 each independently represents an optionally substituted aromatic hydrocarbon ring, an optionally substituted aromatic heterocyclic ring, or a fused ring containing these ring structures and optionally having substituents. Ring B 1 and Ring B 2 each independently represents a hydrocarbon ring optionally having substituents and / or a fused ring structure, or a heterocyclic ring optionally having substituents and / or a fused ring structure, and is spiro-bonded to an adjacent pyrrole ring R 1 and R 2 each independently represents an organic group, L represents a methylene chain having 5 to 9 carbon atoms, and each of the methylenes contained in the methylene chain is independently optionally substituted, and the substituents are optionally linked to each other. X - Represents a monovalent anion with a pKa of the conjugate acid of -8.0 or less.

2. The cyanine compound according to claim 1, wherein The ring B 1 and the ring B 2 are hydrocarbon rings having a fused-ring structure or heterocyclic rings having a fused-ring structure.

3. The cyanine compound according to claim 1, wherein, The ring B 1 and the ring B 2 have 5 or 6 ring members in the hydrocarbon or heterocyclic ring that is spiro-bonded to the adjacent pyrrole ring.

4. The cyanine compound according to claim 1, wherein The ring B 1 and the ring B 2 are hydrocarbon rings or heterocyclic rings represented by the following formulas (2-1) to (2-4): [Chemical formula 2] In formulas (2-1) to (2-4), Ring C 1 ~Ring C 6 Each independently represents an optionally substituted hydrocarbon ring, Y 1 represents -CH2-, -NH-, -O- or -S- Y 2 ~Y 6 each independently represents -CH2-, -CH═, -NH-, -N═, -O- or -S- * represents the site of spiro bonding to the adjacent pyrrole ring.

5. A resin composition, characterized in that, Comprising the cyanine compound according to any one of claims 1 to 4 and a resin component.

6. The resin composition according to claim 5, wherein, The resin composition further comprises a solvent.

7. An ink liquid composition, characterized in that, Comprising the cyanine compound according to any one of claims 1 to 4 and a solvent.

8. A filter, characterized in that, Having a resin layer formed from the resin composition according to claim 5.

9. A method for manufacturing a nitrogen-containing heterocyclic compound, characterized in that, Including a step of reacting a compound represented by the following formula (5) with an alkylating agent represented by the following formula (6) to obtain a compound represented by the following formula (4), [Chemical formula 3] In formulas (4) to (6), Ring A 1 represents an optionally substituted aromatic hydrocarbon ring, an optionally substituted aromatic heterocyclic ring, or a fused ring containing these ring structures and optionally having substituents Ring B 1 represents a hydrocarbon ring optionally having substituents and / or a fused ring structure, or a heterocyclic ring optionally having substituents and / or a fused ring structure, which is spiro-bonded to the adjacent pyrrole ring R 1 represents an alkyl group Z represents an atom or group that provides a monovalent anion.

10. The method for producing a nitrogen-containing heterocyclic compound according to claim 9, wherein The said R 1 is methyl, The alkylating agent is halogenated methane or methyl sulfonate, The said Z - is a halide ion or a sulfonate ion.

11. A nitrogen-containing heterocyclic compound, characterized in that, represented by the following formula (4): [Chemical formula 4] In formula (4), Ring A 1 represents an optionally substituted aromatic hydrocarbon ring, an optionally substituted aromatic heterocyclic ring, or a fused ring containing these ring structures and optionally having substituents Ring B 1 represents a hydrocarbon ring optionally having substituents and / or a fused ring structure, or a heterocyclic ring optionally having substituents and / or a fused ring structure, and is spiro-bonded to an adjacent pyrrole ring R 1 represents an organic group Z - represents a halide ion or a sulfonate ion.

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