Novel compound, near-infrared absorbing dye, near-infrared absorbing composition, and optical filter

Abstract

To provide a compound which has a high transmittance in a specific region of near-infrared (900 nm-1200 nm), excellent ability of cutting near-infrared of 700 nm-800 nm, and good heat resistance.SOLUTION: The invention provides a complex salt obtained by reacting a compound represented by the formula in the figure with a metal salt in a solvent. (In the formula, X41 to X48 are each independently H, an alkyl group, or the like.)SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a novel compound, a near-infrared absorbing dye, a near-infrared absorbing composition, and an optical filter. [Background technology]

[0002] Near-infrared absorbing materials are used in a wide range of applications, such as near-infrared absorbing films that block heat rays, near-infrared absorbing plates, agricultural near-infrared absorbing films that selectively utilize sunlight, recording media that utilize heat absorbed by near-infrared rays, near-infrared cut filters for electronic devices, near-infrared filters for photography, protective glasses, sunglasses, heat-shielding films, dyes for optical recording, optical character reading and recording, confidential document copy prevention, electrophotographic photoreceptors, and laser fusion.

[0003] In particular, solid-state imaging devices (CCD image sensors, CMOS image sensors, etc.) used in digital cameras, smartphones, etc. may detect near-infrared light as noise when external light enters the light-receiving section that is sensitive to it, so sensitivity correction is sometimes performed by cutting out specific near-infrared light with an optical filter.

[0004] In addition, in recent years, attempts have been made to add sensing functions (motion capture, spatial recognition, biometric authentication, etc.) that utilize near-infrared light to camera modules. For example, when using a near-infrared LED of 900 nm or 940 nm as detection light, the optical filter may be required to be transparent to these detection wavelengths.

[0005] Thus, there is a need for near-infrared absorbing materials that selectively transmit visible light and some near-infrared light, rather than blocking near-infrared light as in the past.

[0006] Known near-infrared absorbing dyes include phthalocyanine dyes, cyanine dyes, diimonium dyes, squarylium dyes, croconium dyes, and indigo dyes. Among these, phthalocyanine dyes and cyanine dyes are particularly representative. Each has its own distinctive characteristics. Phthalocyanine dyes have a relatively robust structure, resulting in good resistance to various types of light. However, they have poor transparency and invisibility due to absorption in the visible light region caused by a structure called the Soret band. On the other hand, cyanine dyes are generally used in a dissolved state as dyes, resulting in very high transparency and invisibility, but they have significantly poor resistance to various types of light, especially lightfastness. Diimonium dyes, squarylium dyes, and croconium dyes also have characteristics similar to those of cyanine dyes.

[0007] As an indigo dye-based compound, a boron compound is disclosed in Patent Document 1. Also, a palladium complex is disclosed in Patent Document 2. However, these compounds do not combine absorption in the near-infrared region with high heat resistance. [Prior art documents] [Patent documents]

[0008] [Patent Document 1] Japanese Patent Application Laid-Open No. 2012-224593 [Patent Document 2] Japanese Patent Application Laid-Open No. 2013-87233 Summary of the Invention [Problem to be solved by the invention]

[0009] The present invention has high transmittance in the near-infrared region (900 nm to 1200 nm), and The present invention aims to provide a compound having excellent near-infrared absorbing ability in the range of 1000 to 800 nm and good heat resistance. Another object of the present invention is to provide a near-infrared absorbing dye, a near-infrared absorbing composition, and an optical filter having good dispersion stability and light resistance. [Means for solving the problem]

[0010] As a result of extensive research to solve the above-mentioned problems, the inventors have found that the compounds represented by general formula (1) or general formula (2) have high transmittance of near-infrared rays in a specific range (900 nm to 1200 nm), excellent ability to cut near-infrared rays in the range of 700 nm to 800 nm, and good heat resistance, thereby completing the present invention.

[0011] That is, the present invention relates to a compound represented by general formula (1) or general formula (2). [ka] [In the formula, X1~X 40 each independently represents a hydrogen atom or an alkyl group which may have a substituent. group, an optionally substituted aryl group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted arylalkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an amino group, an optionally substituted alkylamino group, an optionally substituted arylamino group, a cyano group, a halogen atom, a nitro group, a hydroxyl group, -SO3H; -COOH; and monovalent to trivalent groups of these acidic groups. Metal salts; alkylammonium salts. X1~X 40 Two adjacent groups among the groups represented by the formula (I) may be linked to form a 5- or 6-membered ring together with the carbon atoms to which they are attached. M represents a metal atom.

[0012] The present invention also relates to the above compound, wherein M is a divalent metal atom.

[0013] The present invention also relates to a near-infrared absorbing dye comprising the compound.

[0014] The present invention also relates to a near-infrared absorbing composition comprising the near-infrared absorbing dye and a binder resin.

[0015] The present invention also relates to the near-infrared absorbing composition, wherein the water content in the near-infrared absorbing composition is 0.1 to 2.0% by mass based on the total mass of the near-infrared absorbing composition.

[0016] The present invention also relates to the near infrared absorbing composition, which contains a metal component including a metal atom selected from Li, Na, K, Cs, Ca, Fe, and Zr, and wherein the total amount of the metal atoms in the metal component is 1 to 1000 ppm by mass with respect to the entire near infrared absorbing composition.

[0017] The present invention also relates to the near-infrared absorbing composition, which further contains a photopolymerizable monomer and / or a photopolymerization initiator.

[0018] The present invention also relates to the near-infrared absorbing composition, which contains an organic dye having absorption in the range of 400 nm to 700 nm.

[0019] The present invention also relates to an optical filter comprising a substrate and a coating formed from the near-infrared absorbing composition. [Effects of the Invention]

[0020] The present invention provides a compound that has high transmittance for near-infrared rays in a specific region (900 nm to 1200 nm) and excellent ability to cut near-infrared rays from 700 nm to 800 nm. Furthermore, when the compound is used as a near-infrared absorbing dye, it is possible to provide a near-infrared absorbing composition and an optical filter that have good dispersion stability, light resistance, and heat resistance. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 is an infrared absorption spectrum of the compound (a) produced in Example 1. [Figure 2]FIG. 2 is an infrared absorption spectrum of the compound (b) produced in Example 2. [Figure 3] FIG. 3 is an infrared absorption spectrum of the compound (c) produced in Example 3. [Figure 4] FIG. 4 is an infrared absorption spectrum of the compound (d) prepared in Example 4. [Figure 5] FIG. 5 is an infrared absorption spectrum of the compound (e) prepared in Example 5. [Figure 6] FIG. 6 is an infrared absorption spectrum of the compound (q) prepared in Example 17. [Figure 7] FIG. 7 is an infrared absorption spectrum of the compound (s) prepared in Example 19. DETAILED DESCRIPTION OF THE INVENTION

[0022] The terms used in this specification are defined below. Unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" refer to "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively. "CI" used in this specification refers to the Color Index (CI). Colorants include pigments and dyes.

[0023] <Compounds represented by general formula (1) or general formula (2)> The compounds of the present invention represented by general formula (1) or general formula (2) will be explained below. [ka] [In the formula, X1~X 40are each independently a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted arylalkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an amino group, an optionally substituted alkylamino group, an optionally substituted arylamino group, a cyano group, a halogen atom, a nitro group, a hydroxyl group, -SO3H; -COOH; and monovalent to trivalent groups of these acidic groups. Metal salts; alkylammonium salts. X1~X 40 Two adjacent groups among the groups represented by the formula (I) may be linked to form a 5- or 6-membered ring together with the carbon atoms to which they are attached. M represents a metal atom.

[0024] Examples of the "alkyl group" in the alkyl group which may have a substituent include a straight-chain or branched alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, an n-octyl group, a stearyl group, a 2-ethylhexyl group, etc. Examples of the "alkyl group having a substituent" include a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, a 2,4-dichlorobenzyl group, etc.

[0025] Examples of the "aryl group" of the aryl group which may have a substituent include a phenyl group, a naphthyl group, an anthryl group, and the like. Examples of the "substituted aryl group" include a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, Examples include a pentafluorophenyl group, a 2-aminophenyl group, a 2-methyl-4-chlorophenyl group, a 4-hydroxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, and a 2-aminoanthraquinonyl group.

[0026] Examples of the "alkoxyl group" in the alkoxyl group which may have a substituent include linear or branched alkoxyl groups such as a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyloxy group, a 2,3-dimethyl-3-pentyloxy group, an n-hexyloxy group, an n-octyloxy group, a stearyloxy group, and a 2-ethylhexyloxy group. Examples of the "substituted alkoxyl group" include a trichloromethoxy group, a trifluoromethoxy group, a 2,2,2-trifluoroethoxy group, a 2,2,3,3-tetrafluoropropoxy group, a 2,2-ditrifluoromethylpropoxy group, a 2-ethoxyethoxy group, a 2-butoxyethoxy group, a 2-nitropropoxy group, and a benzyloxy group.

[0027] Examples of the "aryloxy group" of the aryloxy group which may have a substituent include a phenoxy group, a naphthoxy group, an anthryloxy group, etc., and examples of the "aryloxy group having a substituent" include a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, a 2-methyl-4-chlorophenoxy group, etc.

[0028] Examples of the "arylalkyl group which may have a substituent" include a benzyl group, a 2-phenylpropan-yl group, a styryl group, a diphenylmethyl group, and a triphenylmethyl group.

[0029] Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group, etc. Examples of the "cycloalkyl group having a substituent" include a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group, etc.

[0030] Examples of the "alkylthio group" of the alkylthio group which may have a substituent include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a pentylthio group, a hexylthio group, an octylthio group, a decylthio group, a dodecylthio group, and an octadecylthio group. Examples of the "substituted alkylthio group" include a methoxyethylthio group, an aminoethylthio group, a benzylaminoethylthio group, a methylcarbonylaminoethylthio group, and a phenylcarbonylaminoethylthio group.

[0031] Examples of the "arylthio group" of the arylthio group which may have a substituent include a phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, and a 9-anthrylthio group. Examples of the "substituted arylthio group" include a chlorophenylthio group, a trifluoromethylphenylthio group, a cyanophenylthio group, a nitrophenylthio group, a 2-aminophenylthio group, and a 2-hydroxyphenylthio group.

[0032] Examples of the "alkylamino group" in the alkylamino group which may have a substituent include a methylamino group, an ethylamino group, a propylamino group, a butylamino group, a pentylamino group, a hexylamino group, a heptylamino group, an octylamino group, a nonylamino group, a decylamino group, a dodecylamino group, an octadecylamino group, an isopropylamino group, an isopentylamino group, a sec-butylamino group, a tert-butylamino group, a sec-pentylamino group, a tert-pentylamino group, a tert-octylamino group, a neopentylamino group, a cyclopropylamino group, a cyclobutylamino group, a cyclopentyl ... Examples of such an amino group include a cyclohexylamino group, a cycloheptylamino group, a cyclooctylamino group, a cyclododecylamino group, a 1-adamantamino group, and a 2-adamantamino group.

[0033] Examples of the "arylamino group" of the arylamino group which may have a substituent include an anilino group, a 1-naphthylamino group, a 2-naphthylamino group, an o-toluidino group, a m-toluidino group, a p-toluidino group, a 2-biphenylamino group, a 3-biphenylamino group, a 4-biphenylamino group, a 1-fluoreneamino group, a 2-fluoreneamino group, a 2-thiazoleamino group, and a p-terphenylamino group.

[0034] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

[0035] Examples of the acidic group include -SO3H and -COOH, and the monovalent to trivalent metals of these acidic groups Examples of the salt include sodium salt, potassium salt, magnesium salt, calcium salt, iron salt, aluminum salt, etc. Examples of the alkylammonium salt of an acidic group include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, and stearylamine, and quaternary alkylammonium salts such as palmityltrimethylammonium, lauryltrimethylammonium, dilauryldimethylammonium, and distearyldimethylammonium salt.

[0036] X1~X 40Two adjacent groups among the groups represented by the formula (I) may be linked to form a 5- or 6-membered ring together with the carbon atoms to which they are bonded. The 5- or 6-membered ring may have a substituent. Examples of such 5-membered rings include a cyclopentene ring, a cyclopentadiene ring, an imidazole ring, a thiazole ring, a pyrazole ring, an oxazole ring, an isoxazole ring, a thiophene ring, a furan ring, and a pyrrole ring. Examples of 6-membered rings include a cyclohexane ring, a cyclohexene ring, a cyclohexadiene ring, a benzene ring, a pyridine ring, a piperazine ring, a piperidine ring, a morpholine ring, a pyrazine ring, a pyrone ring, and a pyrrolidine ring.

[0037] Among the above substituents, X1 to X 40 Preferred substituents for include a hydrogen atom, a methyl group, a methoxy group, a fluorine atom, a chlorine atom, a bromine atom, and -SO3H.

[0038] M represents a metal atom. Examples of metal atoms include Zn, Co, Ni, Ru, Pt, Mn, Sn, Ti, and Ba. Among these, divalent metal atoms are preferred, and Zn, Co, and Ni are more preferred. By forming a dimer represented by general formula (1) or a trimer represented by general formula (2), a compound with good heat resistance is obtained.

[0039] (Method for synthesizing compounds represented by general formula (1) or general formula (2)) The synthesis method of the compound represented by general formula (1) or general formula (2) is described below. The compound represented by general formula (1) or general formula (2) can be obtained by reacting the compound represented by general formula (3) with a metal salt in a solvent. The compound represented by general formula (3) can be obtained according to the synthesis method described in JP 2012-224593 A.

[0040] General formula (3) [ka] [where, X 41 ~X 48 is X1~X40 is equivalent to.]

[0041] Examples of the metal salts used as raw materials include acetates, acetylacetone complexes, and metal halides.

[0042] The reaction temperature is not particularly limited, but is preferably in the range of 20 to 120°C, more preferably 20 to 50°C.

[0043] The reaction solvent is not particularly limited, but is preferably one in which the intermediate and metal salt are soluble, and specific examples include tetrahydrofuran, toluene, and N-methylpyrrolidone.

[0044] The amount of the metal salt used is 0.5 moles or more, and preferably 1.0 to 3.0 moles, per mole of the compound represented by formula (3).

[0045] The reaction time is not particularly limited, but the progress of the reaction may be confirmed by MALDI TOF-MS spectroscopy or a spectrophotometer to confirm the disappearance of the raw materials.

[0046] In the production of compounds represented by general formula (1) or (2), compounds represented by general formula (1) (hereinafter referred to as dimer) and general formula (2) (hereinafter referred to as trimer) are produced as a mixture, and TOF-MS spectra confirm that compounds represented by general formula (4) (hereinafter referred to as tetramer) are produced as a minor component. The production ratio of dimer, trimer, and tetramer was determined by calculating the peak intensity (relative intensity) of each molecular ion relative to the sum of all molecular ion peak intensities in the TOF-MS spectrum, and the relative intensity ratio was considered to be the molar ratio.

[0047] General formula (4) [ka] [where, X 49 ~X 80 is X1~X 40 is equivalent to.]

[0048] During synthesis, if the molar ratio of the metal salt to the compound represented by general formula (3) is high, the ratio of trimers produced will be high. The molar ratio of tetramers is preferably 30.0 mass% or less based on the total molecules of the compound produced.

[0049] The compounds represented by general formula (1) or (2) have absorption in a specific near-infrared region (700 nm to 800 nm) and little absorption in the visible light region (480 nm to 650 nm), and therefore, when used as near-infrared absorbing dyes, they function excellently as near-infrared absorbents.

[0050] In the present invention, examples of the compound represented by general formula (1) include the following compounds, but the present invention is not limited to these.

[0051] [ka] JPEG0007810015000006.jpg255169

[0052] In the present invention, examples of the compound represented by general formula (2) include the following compounds, but the present invention is not limited to these.

[0053] [ka] JPEG0007810015000008.jpg71170

[0054] <Near-infrared absorbing dye> The near-infrared absorbing dye of the present invention is characterized by containing a compound represented by general formula (1) or general formula (2).

[0055] <Other near-infrared absorbing dyes> The near-infrared absorbing dye of the present invention may contain other near-infrared absorbing dyes in addition to the compounds represented by general formulas (1), (2), and (4). This allows the spectrum to be adjusted appropriately. Examples of other near-infrared absorbing dyes include cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, anthraquinone compounds, aminium compounds, diimmonium compounds, indigo compounds (excluding the compounds represented by general formulas (1), (2), and (4)), croconium compounds, azo compounds, quinoid complex compounds, and dithiol metal complex compounds.

[0056] <Near-infrared absorbing composition> The near-infrared absorbing composition of the present invention is characterized by containing a near-infrared absorbing dye containing a compound represented by general formula (1) or general formula (2), and a binder resin.

[0057] The content of the compound represented by general formula (1) or general formula (2) of the present invention is preferably in the range of 2 to 70 mass % based on the total weight (100 mass %) of the near-infrared absorbing composition. When other near-infrared absorbing dyes are used in combination as the near-infrared absorbing dye, the weight ratio of other near-infrared absorbing dyes to the compound represented by general formula (1) or general formula (2) is preferably in the range of 5 / 95 to 50 / 50.

[0058] <Organic dyes with absorption in the 400nm to 700nm range> The near-infrared absorbing composition of the present invention can contain an organic dye other than the near-infrared absorbing dye of the present invention, which has absorption in the range of 400 nm to 700 nm. The compound represented by general formula (1) or general formula (2) contained in the near-infrared absorbing composition of the present invention has strong absorption in the range of 700 nm to 800 nm. Therefore, by including, for example, a black organic dye or an organic dye that exhibits black by combining multiple organic dyes, the composition can be used as a near-infrared transmitting composition that blocks light rays of 400 nm to 800 nm and transmits light of 800 nm or more. In addition ... By including an organic dye with absorption in a specific region of 400 to 700 nm to match the wavelength of the light source, it can be used as a near-infrared absorbing composition that blocks external unwanted light and improves sensing accuracy. However, to ensure transmittance above 800 nm, it is necessary to use an organic dye with low absorption above 800 nm.

[0059] Examples of organic dyes that have absorption in the range of 400 nm to 700 nm include blue dyes, green dyes, yellow dyes, purple dyes, and red dyes. The organic colorant may be an organic pigment, and examples thereof include diketopyrrolopyrrole pigments, azo pigments such as azo, disazo, or polyazo, anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthanthrone, indanthrone, pyranthrone, or violanthrone, quinacridone pigments, perinone pigments, perylene pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, phthalocyanine pigments, threne pigments, and metal complex pigments. Furthermore, dyes may be used as the organic colorant, and examples thereof include anthraquinone dyes, monoazo dyes, disazo dyes, oxazine dyes, aminoketone dyes, xanthene dyes, quinoline dyes, and triphenylmethane dyes. When using dyes, it is effective to incorporate the polar groups of anionic or cationic dyes into the resin to impart solubility in organic solvents.

[0060] (blue pigment) Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79.

[0061] Blue dyes include CI Acid Blue 1, 2, 3, 4, 5, 6, 7, 8, 9, 11, 13, 14, 15, 17, 19, 21, 22, 23, 24, 25, 26, 27, 29, 34, 35, 37, 40, 41, 41:1, 43, 44, 45, 46, 47, 48, 49, 50, 51, and 52. , 53, 54, 55, 56, 57, 58, 62, 62:1, 63, 64, 65, 68, 69, 70, 73, 75, 78, 79, 80, 81, 83, 8485, 86, 88, 89, 90, 90:1, 91, 92, 93, 95, 96, 99, 100, 103, 104, 108, 109, 11 0, 111, 112, 113, 114, 116, 117, 118, 119, 120, 123, 124, 127, 127:1, 128, 129, 135, 137, 138, 143, 145, 147, 150, 155, 159, 169, 174, 175, 176, 183, 198, 203 , 204, 205, 206, 208, 213, 227, 230, 231, 232, 233, 235, 239, 245, 247, 253, 257, 258, 260, 261, 262, 264, 266, 269, 271, 272, 273, 274, 277, 278, 280, etc.

[0062] Also, CI Direct Blue 1, 2, 3, 4, 6, 7, 8, 8:1, 9, 10, 12, 14, 15, 16, 19, 20, 21, 21:1, 22, 23, 25, 27, 29, 31, 35, 36, 37, 40, 42, 45, 48, 49, 50, 53, 54, 55, 58, 60, 61, 64, 65, 67, 79, 96, 97, 98:1, 101, 106, 107, 108, 109, 111, 116, 122, 123, 124, 128, 129, 130 , 130:1, 132, 136, 138, 140, 145, 146, 149, 152, 153, 154, 156, 158, 158:1, 164, 165, 166, 167, 168, 169, 170, 174, 177, 181, 184, 185, 188, 190, 192, 193, 206, 207, 209, 213, 215, 225, 226, 229, 230, 231, 242, 243, 244, 253, 254, 260, 263, etc. .

[0063] (green pigment) Examples of green pigments include CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Green 62, and CI Pigment Green 63.

[0064] Examples of green dyes include CI Solvent Green 3, 20, and 28, CI Acid Green 25, 27, 36, 37, 38, 41, 42, and 44, and CI Vat Green 3, 6, and 8.

[0065] (yellow pigment) Examples of yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, and 136. , 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 231, 233, 234, etc.

[0066] Yellow dyes include CI Acid Yellow 2, 3, 4, 5, 6, 7, 8, 9, 9:1, 10, 11, 11:1, 12, 13, 14, 15, 16, 17, 17:1, 18, 20, 21, 22, 23, 25, 26, 27, 29, 30, 31, 33, 34, 36, 38, 39, 40, 40:1, 41, 42, 42:1, 43, 44, 46, 48, 51, 53, 55, 56, 60, 63, 65, and 66. , 67, 68, 69, 72, 76, 82, 83, 84, 86, 87, 90, 94, 105, 115, 117, 122, 127, 131, 132, 136, 141, 142, 143, 144, 145, 146, 149, 153, 159, 166, 168, 169, 172, 174, 175, 178, 180, 183, 187, 188, 189, 190, 191, 192, 199, etc.

[0067] Further examples include CI Direct Yellow 1, 2, 4, 5, 12, 13, 15, 20, 24, 25, 26, 32, 33, 34, 35, 41, 42, 44, 44:1, 45, 46, 48, 49, 50, 51, 61, 66, 67, 69, 70, 71, 72, 73, 74, 81, 84, 86, 90, 91, 92, 95, 107, 110, 117, 118, 119, 120, 121, 126, 127, 129, 132, 133, and 134.

[0068] (purple pigment) Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0069] Purple dyes include CI Acid Violet 1, 2, 3, 4, 5, 5:1, 6, 7, 7:1, 9, 11, 12, 13, 14, 15, 16, 17, 19, 20, 21, 23, 24, 25, 27, 29, 30, 31, 33, 34, 36, 38, 39, 41, 42, 43, 47, 49, 51, 63, 67, 72, 76, 96, 97, 102, 103, 109, etc.

[0070] Further examples include CI Direct Violet 1, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 16, 17, 18, 21, 22, 25, 26, 27, 28, 29, 30, 31, 32, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 45, 51, 52, 54, 57, 58, 61, 62, 63, 64, 71, 72, 77, 78, 79, 80, 81, 82, 83, 85, 86, 87, 88, 93, and 97.

[0071] (red pigment) Examples of red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 10 1, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 222:1, 224, 226, 228, 229, 230, 231, 232, 233, 234, 235, 236, 237, 238, 239, 240, 241, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 253, 254, 255, 256, 257, 258, 259, 260, 261, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 1 0, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 291, 295, 296, etc.

[0072] Orange pigments that work similarly to red pigments include CI Pigment Orange. Orange pigments such as Orange 36, 38, 43, 51, 55, 59, 61, and 73 can be used.

[0073] Red dyes include CI Acid Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 23, 24, 25, 25:1, 26, 26:1, 26:2, 27, 29, 30, 31, 32, 33, 34, 35, 36, 37, 39, 40, 41, 42, 43, 44, 45, 47, 50, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 3, 54, 55, 56, 57, 59, 60, 62, 64, 65, 66, 67, 68, 70, 71, 73, 74, 76, 76:1, 80, 81, 82, 83, 85, 86, 87, 88, 89, 91, 92, 93, 97, 99, 102, 104, 106, 107, 108, 110, 111, 113, 114, 115, 116, 120, 123, 125, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 178, 179, 180, 181, 182, 183, 184, 185, 186, 187, 18 28, 131, 132, 133, 134, 135, 137, 138, 141, 142, 143, 144, 148, 150, 151, 152, 154, 155, 157, 158, 160, 161, 163, 164, 167, 170, 171, 172, 173, 175, 176, 177, 181, 229, 231, 237, 239, 240, 241, 242, 243 9, 252, 253, 255, 257, 260, 263, 264, 266, 267, 274, 276, 280, 286, 289, 299, 306, 309, 311, 323, 333, 324, 325, 326, 334, 335, 336, 337, 340, 343, 344, 347, 348, 350, 351, 353, 354, 356, 388, etc.

[0074] Also, CI Direct Red 1, 2, 2:1, 4, 5, 6, 7, 8, 10, 10:1, 13, 14, 15, 16, 17, 18, 21, 22, 23, 24, 26, 26:1, 28, 29, 31, 33, 33:1, 34, 35, 36, 37, 39, 42, 43, 43:1, 44, 46, 47, 48, 49, 50, 51, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 13 9, 52, 53, 54, 55, 56, 57, 58, 59, 60, 61, 62, 67, 67:1, 68, 72, 72:1, 73, 74, 75, 77, 78, 79, 81, 81:1, 85, 86, 88, 89, 90, 97, 100, 101, 101:1, 107, 108, 110, 114 , 116, 117, 120, 121, 122, 122:1, 124, 125, 127, 127:1, 127:2, 128, 129, 130, 132, 134, 135, 136, 137, 138, 140, 141, 148, 149, 150, 152, 153, 154, 155, 156, 169, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 186, 189, 204, 211, 213, 214, 217, 222, 224, 225, 226, 227, 228, 232, 236, 237, 238, and the like.

[0075] Other examples include CI Solvent Red 52, 135, 146, 149, 168, 179, 207, and the like.

[0076] Although the above dyes have good spectral characteristics and excellent color development, they have problems with light resistance and heat resistance, and their characteristics may not be sufficient for use in optical filters. Therefore, in order to overcome these drawbacks, when the dye is in the form of a basic dye, it is preferable to use an organic acid or perchloric acid to form a salt. As the organic acid, it is preferable to use an organic sulfonic acid or an organic carboxylic acid. Among them, it is preferable to use a naphthalenesulfonic acid such as Tobias acid or perchloric acid in terms of resistance. It is also preferable to use a resin having an anionic group and form a salt therewith, and it is also preferable to use a resin having a betaine structure and form a salt therewith with an organic acid. In the case of anionic dyes including acid dyes and direct dyes, it is preferable to use a salt-forming compound in which a compound having a cationic group or a resin having a cationic group is used as a counter ion, in terms of heat resistance, light fastness, and solvent resistance. It is also preferable to use a resin having a cationic group and form a salt therewith, and it is more preferable to use a resin having a cationic group on the side chain and form a salt therewith with an organic acid. In addition, it is also preferable in terms of durability to use an anionic dye as a sulfonamidated sulfonic acid amide compound. For coating applications, it is preferable to use CI Pigment Blue 15:3 or Pigment Blue 15:6 as the blue pigment, CI Pigment Yellow 139 as the yellow pigment, and CI Pigment Violet 23 as the purple pigment. For molding applications, it is preferable to use CI Pigment Blue 15:3 or Pigment Blue 15:6 as the blue pigment, CI Pigment Yellow 147 as the yellow pigment, and CI Solvent Red 52 as the red pigment.

[0077] <Specific metal atoms> The near-infrared absorbing composition of the present invention may contain small amounts of metal components including Li, Na, K, Cs, Mg, Ca, Fe, and Zr (hereinafter also referred to as specific metal atoms) in addition to the constituent components of the compound represented by general formula (1) or general formula (2) and the organic dye. If a large amount of metal components including these specific metal atoms is present, storage stability may be impaired, heat resistance may be reduced, or sensitivity may be reduced when the composition is prepared in the form of a photosensitive near-infrared absorbing composition described below. Furthermore, an optical filter produced using a near-infrared absorbing composition containing a large amount of metal components containing such specific metal atoms may generate foreign matter, which may result in a decrease in transmittance. The total content of the specific metal atoms in the metal components contained in the near-infrared absorbing composition of the present invention is preferably 1 to 1,000 ppm by mass with respect to the entire near-infrared absorbing composition.

[0078] The total amount of specific metal atoms contained in the near-infrared absorbing composition of the present invention is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less, based on the entire near-infrared absorbing composition.In addition, the lower limit of the total amount of specific metal atoms is not particularly limited, but is preferably 1 mass ppm or more, more preferably 5 mass ppm or more, based on the entire near-infrared absorbing composition.If it is within the above range, it is possible to obtain a near-infrared absorbing composition that can reduce costs, has excellent storage stability, and can form an optical filter with little generation of foreign matter and little decrease in transmittance.

[0079] The content of each specific metal atom contained in the near infrared absorbing composition of the present invention is preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less, based on the entire near infrared absorbing composition.

[0080] Furthermore, when metal atoms M in the compound represented by general formula (1) or general formula (2) or metal atoms such as Ni, Zn, Pt, Mn, and Co are contained as part of the organic dye structure, these metal atoms may be present but not part of the compound or organic dye structure. The fewer such metal atoms, the better, and they can be removed in the same way as specific metal atoms by the method described below. Furthermore, it is also preferable that the concentrations of Cs, Ti, Si, Pd, and other elements that are mixed in due to materials (e.g., catalysts) used in the manufacturing process of various raw materials for the near-infrared absorbing composition are low.

[0081] Methods for removing metal atoms that have been mixed into the various raw materials contained in the near-infrared absorbing composition or that have been mixed in from the equipment during the manufacturing process include methods using water washing as described in JP-A Nos. 2010-83997, 2018-36521, 7-198928, 8-333521, and 2009-7432, and methods such as removing magnetic foreign matter using a magnet as described in JP-A No. 2011-48736, and these methods can be used alone or in combination as appropriate.

[0082] The content of specific metal atoms can be measured by inductively coupled plasma emission spectroscopy (ICP).

[0083] <Dye derivatives> The near-infrared absorbing composition of the present invention may contain a dye derivative as needed. The dye derivative is a compound having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. Examples of the dye derivative include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, as well as amine salts thereof, sulfonamide groups, or compounds having basic substituents such as a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group. Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0084] Specifically, diketopyrrolopyrrole dye derivatives are disclosed in JP 2001-220520 A, WO2009 / 081930 A, WO2011 / 052617 A, WO2012 / 102399 A, and JP 2017-156397 A, phthalocyanine dye derivatives are disclosed in JP 2007-226161 A, WO2016 / 163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A, and anthraquinone dye derivatives are disclosed in JP 63-264674 A, JP 2009-2006062 A, and Japanese Patent No. 2009-2009062 A, and JP-A-9-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009 / 025325 pamphlet; quinacridone dye derivatives are disclosed in JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383; dioxazine dye derivatives are disclosed in JP-A-20 Thiazine indigo dye derivatives are disclosed in JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681, and Benzoisoindole dye derivatives are disclosed in JP 2009-57478 A, quinophthalone dye derivatives are disclosed in JP 2003-167112 A, JP 2006-291194 A, JP 2008-31281 A, and JP 2012-226110 A, naphthol dye derivatives are disclosed in JP 2012-208329 A, JP 2014-5439 A, and Examples of the zo-based dye derivatives include those described in JP-A Nos. 2001-172520 and 2012-172092, those with acidic substituents include those described in JP-A No. 2004-307854, and those with basic substituents include those described in JP-A Nos. 2002-201377, 2003-171594, 2005-181383, and 2005-213404. Note that these documents may refer to dye derivatives as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds, but the compounds having a substituent such as an acidic group, a basic group, or a neutral group in the organic dye residue are synonymous with dye derivatives.

[0085] These dye derivatives can be used alone or in combination of two or more.

[0086] The dye derivative is preferably added in an amount of 1 to 100% by mass, more preferably 3 to 70% by mass, and even more preferably 5 to 50% by mass, relative to 100% by mass of the dye.

[0087] When the colorant is a pigment, by adding a colorant derivative and carrying out a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, or solvent salt milling, the colorant derivative is adsorbed onto the pigment surface, and the primary particles of the pigment can be made finer than when the colorant derivative is not added.

[0088] Adding a dye derivative to a pigment and conducting a dispersion process such as wet dispersion using a two-roll or three-roll roller or beads allows the dye derivative to adsorb to the pigment surface, making the pigment surface polar and promoting the adsorption of the resin-type dispersant. This improves compatibility with the pigment, dye derivative, resin-type dispersant, solvent, and other additives, thereby improving the dispersion stability and viscosity stability over time of the near-infrared absorbing composition. Furthermore, improved compatibility results in excellent coating film stability over time when the near-infrared absorbing composition is applied to a glass substrate or the like, improving the stability and characteristic dependence of pattern shape, etc., on the waiting time from application to exposure (PCD: Post Coating Delay) and the waiting time from exposure to heat treatment (PED: Post Exposure Delay), as well as linewidth sensitivity stability. Furthermore, adsorption and coating of the pigment surface with the dye derivative and resin-type dispersant suppresses pigment aggregation and crystal precipitation due to sublimation when the coating is baked. Furthermore, development time variability and development residue are also suppressed.

[0089] <Resin-type dispersant> The near-infrared absorbing composition of the present invention may contain a resin-type dispersant as needed. The resin-type dispersant has a pigment-affinity moiety that has the property of adsorbing to the pigment and a relaxation moiety that has high affinity with components other than the pigment and causes steric repulsion between dispersed particles. As the resin-type dispersant, a resin with a controlled structure, such as a graft type (comb type) or block type, is preferably used. Among these, a basic resin-type dispersant is preferred.

[0090] Resin-type dispersants include, for example, urethane-based dispersants such as polyurethane, polyaniline, and the like. Examples of suitable polycarboxylic acid esters include polycarboxylic acid esters such as acrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof; amides formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups, and salts thereof; (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc.; polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters.

[0091] Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 142, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, and 215 manufactured by BYK Japan. 0, 2155, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, 21116, 21324 or Lactimon, Lactimon-WS or Bykumen, etc.; SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000 manufactured by Lubrizol Japan Corporation , 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 44 00, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0092] The resin-type dispersants can be used alone or in combination of two or more kinds.

[0093] The content of the resin-type dispersant is preferably 0.1 to 200% by mass, and more preferably 0.1 to 150% by mass, relative to 100% by mass of the pigment. When an appropriate amount is used, good dispersibility can be obtained.

[0094] <Binder resin> The near-infrared absorbing composition of the present invention contains a binder resin. The binder resin is a resin having a transmittance of 80% or more over the entire wavelength range of 400 to 700 nm. The transmittance is preferably 95% or more. In terms of curability, examples of the binder resin include thermoplastic resins, thermosetting resins, and active energy ray-curable resins. The active energy ray-curable resin may be a thermoplastic resin or a thermosetting resin having an active energy ray-reactive functional group. In terms of physical properties, the binder resin is preferably an alkali-soluble resin from the viewpoint of developability. The alkali-solubility is intended to impart development solubility in the alkali development step during the production of an optical filter, and an acidic group is required.

[0095] The binder resins can be used alone or in combination of two or more kinds.

[0096] The content of the binder resin is preferably 20 to 400% by mass relative to 100% by mass of the pigment. A content of 50 to 250 mass % is more preferable. When an appropriate amount is contained, a coating can be easily formed and good color properties can be easily obtained.

[0097] (thermoplastic resin) Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide. resins, etc. Examples of alkali-soluble thermoplastic resins include resins having an acidic group such as a carboxyl group or a sulfonic group. Examples of alkali-soluble thermoplastic resins include acrylic resins having an acidic group, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers. Among these, acrylic resins having an acidic group and styrene / styrene sulfonic acid copolymers are preferred in terms of improving developability, heat resistance, and transparency.

[0098] (active energy ray curable alkali-soluble resin) The active energy ray-curable alkali-soluble resin preferably has an ethylenically unsaturated double bond. The ethylenically unsaturated double bond can be introduced, for example, by the following methods (i) and (ii). The effect of active energy rays is that the resin undergoes three-dimensional cross-linking, increasing the cross-link density and improving chemical resistance.

[0099] [Method (i)] In method (i), for example, an ethylenically unsaturated monomer having an epoxy group is copolymerized with another monomer to obtain a copolymer, and a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is subjected to an addition reaction with the side-chain epoxy group of the copolymer.Then, a polybasic acid anhydride is reacted with the resulting hydroxyl group to introduce the ethylenically unsaturated double bond and the carboxyl group.

[0100] Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acids.

[0101] Examples of unsaturated monobasic acids include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position.

[0102] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. If necessary, for example, to increase the number of carboxyl groups, it is also possible to use a tricarboxylic acid anhydride such as trimellitic anhydride, or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride, and then hydrolyze the remaining anhydride groups.

[0103] Examples of other monomers include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, and isobutyl (meth)acrylate. (meth)acrylates such as t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate; Alternatively, examples include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

[0104] Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6- N-substituted maleimides such as N-(trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine Examples of the ethylene oxide (EO)-modified cresol acrylate include ethylene oxide (EO)-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0105] A method similar to method (i) is, for example, a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of the side chain carboxyl groups of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another monomer, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

[0106] [Method (ii)] Method (ii) is a method in which an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group is reacted with a side chain hydroxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer.

[0107] Examples of the ethylenically unsaturated monomer having a hydroxyl group include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3-, or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Also, hydroxyalkyl (meth)acrylates can be modified with ethylene oxide, propylene oxide, and / or butylene oxide. Examples include polymerized polyether mono(meth)acrylate and polyester mono(meth)acrylate to which poly(γ-valerolactone), poly(ε-caprolactone), and / or poly(12-hydroxystearic acid) are added. From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred, and from the viewpoint of sensitivity, it is preferable to use a compound having 2 to 6 hydroxyl groups, with glycerol mono(meth)acrylate being more preferred.

[0108] Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0109] Other monomers that can be used to form alkali-soluble resins include the other ethylenically unsaturated monomers already described, as well as N-substituted maleimides, alkyleneoxy group-containing monomers, phosphate esters, and the like. Examples of the unsaturated monomer include ethylenically unsaturated monomers containing a ter group and ethylenically unsaturated monomers containing a carboxyl group. Examples of N-substituted maleimides include cyclohexylmaleimide, phenylmaleimide, Methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine. Examples of the alkyleneoxy group-containing monomer include EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0110] The carboxyl group-containing ethylenically unsaturated monomer may be the monomer already described.

[0111] The phosphate group-containing ethylenically unsaturated monomer is, for example, a compound obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0112] (alkali-soluble resin with no ethylenically unsaturated double bond) The near-infrared absorbing composition of the present invention can contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of curing of the coating film.

[0113] In order to impart solubility in alkaline development, the weight-average molecular weight (Mw) of the alkali-soluble resin in the present invention is preferably 4,000 to 100,000, more preferably 5,000 to 50,000. The Mw / Mn value is preferably 10 or less. If the weight-average molecular weight (Mw) is less than 4,000, adhesion to the substrate decreases, making it difficult to retain an exposed pattern. If it exceeds 100,000, solubility in alkaline development decreases, residues are generated, and the linearity of the pattern deteriorates. The acid value of the alkali-soluble resin in the present invention is from 50 to 200 (KOH mg / g) in order to impart alkali development solubility, and is preferably in the range of from 20 to 300, more preferably The acid value is preferably in the range of 90 to 170. If the acid value is less than 50, the solubility in alkaline development decreases, residues are generated, and the linearity of the pattern deteriorates. If the acid value is too high, the adhesion to the substrate decreases, making it difficult to leave an exposed pattern.

[0114] Each raw material used in the synthesis of the binder resin can be used alone or in combination of two or more kinds.

[0115] (thermosetting compound) In the present invention, it is preferable to further contain a thermosetting compound in combination with a thermoplastic resin as a binder resin. For example, when an optical filter is produced using the near-infrared absorbing composition of the present invention, the inclusion of the thermosetting compound reacts during baking of the filter segments to increase the crosslink density of the coating film, thereby improving the heat resistance of the filter segments, suppressing pigment aggregation during baking of the filter segments, and obtaining the effect of suppressing a decrease in transmittance in the range of 480 nm to 650 nm, which is a region with high relative luminous efficiency.

[0116] The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound include, but are not limited to, epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Epoxy compounds and oxetane compounds are preferably used in the near-infrared absorbing composition of the present invention.

[0117] Examples of epoxy compounds include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), and phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, etc.). , divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, glycidylamine epoxy resins, glycidyl ester epoxy resins, etc.

[0118] The content of the thermosetting compound is preferably 0.5 to 300% by mass, more preferably 1.0 to 50% by mass, relative to 100% by mass of the near-infrared absorbing dye of the present invention. When used in an appropriate amount, appropriate heat resistance can be obtained.

[0119] The near-infrared absorbing composition may contain a curing agent or a curing accelerator to aid in the curing of the thermosetting compound. Examples of the curing agent include amine compounds, acid anhydrides, active esters, and carboxylic acids. Examples of the curing accelerator include an amine compound (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), a quaternary ammonium salt compound (e.g., triethylbenzylammonium chloride, etc.), a blocked isocyanate compound (e.g., dimethylamine, etc.), an imidazole derivative bicyclic amidine compound and a salt thereof (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazoline, etc.), a methyl ... Examples of suitable methylimidazole derivatives include methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., phosphorus compounds (e.g., triphenylphosphine, etc.), and S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.).

[0120] The content of the curing agent and the curing accelerator is preferably, for example, 0.01 to 15% by mass each relative to 100% by mass of the thermosetting compound.

[0121] <Photopolymerizable monomer> The near-infrared absorbing composition of the present invention can be made into a photosensitive near-infrared absorbing composition by containing a photopolymerizable monomer and a photopolymerization initiator. The photopolymerizable monomer and the photopolymerization initiator include a monomer or oligomer that is cured by ultraviolet light, heat, or the like to form a transparent resin.

[0122] Examples of the photopolymerizable monomer include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, Examples of suitable acrylic acid esters and methacrylic acid esters include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid esters of methylolated melamine, epoxy (meth)acrylate, and urethane acrylate; (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0123] (Photopolymerizable monomer having an acid group) The photopolymerizable monomer may contain a photopolymerizable monomer having an acid group, such as a sulfonic acid group, a carboxyl group, or a phosphoric acid group.

[0124] Examples of photopolymerizable monomers having an acid group include esters of dicarboxylic acids and poly(meth)acrylates containing free hydroxyl groups, which are polyhydric alcohols and (meth)acrylic acid; and esters of polycarboxylic acids and monohydroxyalkyl(meth)acrylates. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates, such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, with dicarboxylic acids, such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and free carboxyl group-containing oligoesters of tricarboxylic acids, such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid, with monohydroxy monoacrylates or monohydroxy monomethacrylates, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0125] (Photopolymerizable monomer having a urethane bond) The photopolymerizable monomer may contain a photopolymerizable monomer having an ethylenically unsaturated bond and a urethane bond. Examples of the photopolymerizable monomer include a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting the alcohol with a (meth)acrylate having a hydroxyl group.

[0126] Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0127] Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

[0128] The photopolymerizable monomers can be used alone or in combination of two or more kinds.

[0129] The amount of the photopolymerizable monomer is preferably 1 to 50 mass %, more preferably 2 to 40 mass %, based on 100 mass % of the nonvolatile content of the near-infrared absorbing composition. When an appropriate amount is added, the curability and developability are further improved.

[0130] <Photopolymerization initiator> Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, and 2-(dimethylamino)-1-[4-(4-morpholino)phenyl] acetophenone compounds such as 2-(phenylmethyl)-1-butanone or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzo Benzophenone compounds such as 4'-methyldiphenylsulfide or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6- Bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl- triazine compounds such as 4'-methoxystyryl-6-triazine; oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or diphenyl-2,4,6-trimethylbenzoylphosphine oxide;Examples of suitable compounds include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds. Among these, oxime ester compounds are preferred.

[0131] The photopolymerization initiators can be used alone or in combination of two or more.

[0132] (Oxime ester compounds) When oxime ester compounds absorb ultraviolet light, the NO bond of the oxime undergoes cleavage, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, allowing patterns to be formed with a small amount of exposure. When the dye concentration of a near-infrared absorbing composition is high, the ultraviolet transmittance of the coating film may decrease, resulting in a low degree of curing of the coating film. However, oxime ester compounds are preferably used because of their high quantum efficiency.

[0133] Examples of the oxime ester compound include oxime ester photopolymerization initiators described in JP-A Nos. 2007-210991, 2009-179619, 2010-037223, 2010-215575, and 2011-020998.

[0134] The content of the photopolymerization initiator is preferably 2 to 200% by mass, more preferably 2 to 150% by mass, relative to 100% by mass of the dye. When an appropriate amount is added, photocurability and developability are further improved.

[0135] <Sensitizer> Furthermore, the near-infrared absorbing composition of the present invention may contain a sensitizer. Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, Polymethine dyes such as 1,2-diketone derivatives represented by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrin derivatives, Examples of the suitable hydroxybenzoates include pyrazine derivatives, tetraquinoxalylporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 4,4'-bis(diethylamino)benzophenone.

[0136] Among the above sensitizers, particularly suitable sensitizers include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole are used.

[0137] More specifically, examples of sensitizers include, but are not limited to, those described in "Dye Handbook" edited by Makoto Okawara et al. (Kodansha, 1986), "Chemistry of Functional Dyes" edited by Makoto Okawara et al. (CMC, 1981), "Special Function Materials" edited by Chuzaburo Ikemori et al., and "Special Function Materials" (CMC, 1986). In addition, sensitizers that absorb light in the ultraviolet to near-infrared region may also be contained.

[0138] The sensitizers can be used alone or in combination of two or more.

[0139] The content of the sensitizer is preferably 3 to 60% by mass, more preferably 5 to 50% by mass, relative to 100% by mass of the photopolymerization initiator. When an appropriate amount is contained, the curability and developability are further improved.

[0140] <Thiol-based chain transfer agents> The near-infrared absorbing composition of the present invention preferably contains a thiol-based chain transfer agent as a chain transfer agent. By using a thiol together with a photopolymerization initiator, the thiol acts as a chain transfer agent in the radical polymerization process after light irradiation, and generates thiyl radicals that are not easily inhibited by oxygen in polymerization, so that the obtained near-infrared absorbing composition has high sensitivity.

[0141] Also preferred are polyfunctional aliphatic thiols having two or more thiol groups bonded to aliphatic groups such as methylene or ethylene groups. Polyfunctional aliphatic thiols having four or more thiol groups are more preferred. Increasing the number of functional groups improves the polymerization initiation function, allowing curing from the surface of the pattern to the vicinity of the substrate.

[0142] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4- Examples of the thiopropionate include butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0143] The thiol chain transfer agents can be used alone or in combination of two or more.

[0144] The content of the thiol chain transfer agent is preferably 0.1 to 20 mass %, more preferably 0.1 to 10 mass %, based on 100 mass % of the nonvolatile content of the near-infrared absorbing composition. When an appropriate amount is contained, the photosensitivity and tapered shape are improved, and wrinkles are less likely to occur on the coating surface.

[0145] <Polymerization inhibitor> The near-infrared absorbing composition of the present invention may contain a polymerization inhibitor, which can suppress photosensitivity due to diffracted light from a mask during exposure in a photolithography method, making it easier to obtain a pattern with a desired shape.

[0146] Examples of the polymerization inhibitor include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol; alkylresorcinol compounds such as butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucin.

[0147] The content of the polymerization inhibitor is preferably 0.01 to 0.4% by mass relative to 100% by mass of the nonvolatile content of the near-infrared absorbing composition. Within this range, the effect of the polymerization inhibitor is enhanced, resulting in improved tapered linearity, wrinkles in the coating film, pattern resolution, etc.

[0148] <UV absorber> The near-infrared absorbing composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and is, for example, a benzotriazole-based compound, a triazine-based compound, a benzophenone-based compound, a salicylic acid ester-based compound, a cyanoazoline-based compound, a benzophenone-based compound, a salicylic acid ester-based compound, a benzophenone-based compound, a benzophen Examples include acrylate-based compounds and salicylate-based compounds.

[0149] The content of the ultraviolet absorber is preferably 5 to 70% by mass, based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When an appropriate amount is contained, the resolution after development is further improved.

[0150] The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the nonvolatile content of the near-infrared absorbing composition. When an appropriate amount is contained, the adhesion between the substrate and the coating is further improved, and good resolution can be obtained.

[0151] Benzotriazole compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, and 2-(2'-hydroxy-5'-t-octylphenyl) Benzotriazole, a mixture of 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 branched and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3 -(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300 reaction products, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl Examples of suitable hydroxybenzotriazoles include octyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate. Other suitable hydroxybenzotriazoles include oligomeric and polymeric compounds having a benzotriazole structure.

[0152] Triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of suitable triazine compounds include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. Other suitable triazine compounds include oligomers and polymers having a triazine structure.

[0153] Benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxybenzophenone, Examples include 4-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2'-4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc. Oligomeric and polymeric compounds having a benzophenone structure can also be used.

[0154] Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc. Oligomeric and polymeric compounds having a salicylate structure can also be used.

[0155] <Antioxidants> The near-infrared absorbing composition of the present invention may contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the near-infrared absorbing composition from oxidizing and yellowing during the thermal process of thermal curing or ITO annealing, thereby improving the transmittance of the coating film. In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film crosslinking component decreases, and measures such as using a highly sensitive crosslinking component or increasing the amount of photopolymerization initiator are taken, resulting in a phenomenon in which yellowing during the thermal process becomes more severe. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

[0156] Examples of antioxidants include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. Preferably, the antioxidant used in the present invention is a compound that does not contain a halogen atom.

[0157] Among these, from the viewpoint of achieving both transmittance and sensitivity of the coating film, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0158] The antioxidants can be used alone or in combination of two or more kinds.

[0159] Furthermore, when the content of the antioxidant is 0.5 to 5.0% by mass relative to 100% by mass of the solid content of the near-infrared absorbing composition, the transmittance, spectral characteristics, and sensitivity are favorable, and therefore it is more preferable.

[0160] <Amine compounds> The near-infrared absorbing composition may contain an amine compound for reducing dissolved oxygen. Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

[0161] <Leveling agent> The near-infrared absorbing composition may contain a leveling agent to improve the leveling properties of the composition during coating. The leveling agent is preferably, for example, a dimethylsiloxane having a polyether structure or a polyester structure in the main chain. Examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-Chemie Co., Ltd. BYK-333, etc. Examples of dimethylsiloxanes having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. Dimethylsiloxanes having a polyether structure in the main chain and dimethylsiloxanes having a polyester structure in the main chain can be used in combination. The content of the leveling agent is preferably 0.003 to 0.5% by mass relative to 100% by mass of the nonvolatile content of the near-infrared absorbing composition.

[0162] The leveling agent is, for example, a type of surfactant having a hydrophobic group and a hydrophilic group in the molecule, and is a compound that has a hydrophilic group but has low solubility in water and can reduce surface tension. Dimethylpolysiloxane having a polyalkylene oxide unit is preferably used as the leveling agent. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

[0163] The bonding form of the polyalkylene oxide units with the dimethylpolysiloxane may be any of a pendant type in which the polyalkylene oxide units are bonded to the repeating units of the dimethylpolysiloxane, a terminal-modified type in which the polyalkylene oxide units are bonded to the terminals of the dimethylpolysiloxane, and a linear block copolymer type in which the polyalkylene oxide units are bonded alternately and repeatedly to the dimethylpolysiloxane. Dimethylpolysiloxanes having polyalkylene oxide units are commercially available from Dow Corning Toray Co., Ltd., and examples thereof include FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207.

[0164] The leveling agent may contain an anionic, cationic, nonionic, or amphoteric surfactant as an auxiliary. Two or more surfactants may be used in combination.

[0165] Examples of anionic surfactants that can be added auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenyletherdisulfonates, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates.

[0166] Examples of cationic surfactants to be added auxiliary to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of nonionic surfactants to be added auxiliary to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc.; alkyl betaines such as alkyl dimethylaminoacetic acid betaine, amphoteric surfactants such as alkyl imidazolines, and fluorine-based and silicone-based surfactants.

[0167] <Storage stabilizer> The near-infrared absorbing composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer is used in an amount of 0.1 to 10% by mass based on the total amount of colorant (100% by mass). You can be there.

[0168] <Adhesion improver> The near-infrared absorbing composition of the present invention may contain an adhesion improver such as a silane coupling agent to enhance adhesion to the substrate. The improved adhesion due to the adhesion improver improves the reproducibility of fine lines and improves resolution.

[0169] Examples of the adhesion improver include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane and N-2-(aminoethyl)-3- Examples of the silane coupling agent include aminosilanes such as aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercapto compounds such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryl compounds such as p-styryltrimethoxysilane; ureido compounds such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by mass, preferably 0.05 to 5% by mass, relative to 100% by mass of the colorant in the near-infrared absorbing composition. This range is more preferable because the effect is enhanced and a good balance of adhesion, resolution, and sensitivity is achieved.

[0170] <Organic solvents> The near-infrared absorbing composition contains an organic solvent, which makes it easy to adjust the viscosity of the composition.

[0171] Examples of the organic solvent include ethyl lactate, butyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N -Dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether Examples of the alkyl ether include ethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, 4-hydroxy-4-methyl-2-pentanone, N-methylpyrrolidone, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

[0172] Of the above organic solvents, in the case of coating applications, from the viewpoints of coatability and drying property, it is preferable to use an organic solvent having a boiling point at 1 atm of 120° C. or higher and 180° C. or lower. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferred.

[0173] <Method for producing near-infrared absorbing composition> The near-infrared absorbing composition of the present invention can be produced by finely dispersing a pigment in a pigment carrier such as a dispersant or binder resin and / or an organic solvent, preferably together with a dispersing aid (a pigment derivative or a surfactant), using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (pigment dispersion). In this case, two or more pigments may be dispersed simultaneously in the pigment carrier, or they may be dispersed separately in pigment carriers and mixed together. When a pigment such as a dye has high solubility, specifically, when it is highly soluble in the organic solvent used and dissolves by stirring, and no foreign matter is detected, it is not necessary to produce the composition by the above-described fine dispersion method.

[0174] Furthermore, when used as a photosensitive near-infrared absorbing composition (resist material), it can be prepared as a solvent-developable or alkali-developable near-infrared absorbing composition. The solvent-developable or alkali-developable near-infrared absorbing composition can be prepared by mixing the dye dispersion with a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other dispersing aids, additives, etc. The photopolymerization initiator may be added at the stage of preparing the near-infrared absorbing composition, or may be added later to the prepared near-infrared absorbing composition.

[0175] <Removal of large particles> The near-infrared absorbing composition of the present invention is subjected to centrifugation at a gravitational acceleration of 3,000 to 25,000 G, sintering, etc. It is preferable to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably coarse particles of 0.5 μm or more, and mixed dust by means of filtration using a sintered filter or membrane filter. As such, it is preferable that the near-infrared absorbing composition does not substantially contain particles of 0.5 μm or more. More preferably, particles of 0.3 μm or less are preferable.

[0176] <Water content in near-infrared absorbing composition> The near-infrared absorbing composition of the present invention preferably has a water content of 0.1 to 2.0% by mass based on the total mass of the near-infrared absorbing composition.

[0177] When the water content is within the above range, the near-infrared absorbing composition has excellent dispersion stability and sensitivity even after storage over time.

[0178] The water content is preferably 1.8 mass % or less, and more preferably 1.6 mass % or less, based on the total amount of the near-infrared absorbing composition. If the water content is sufficiently small within this range, problems are unlikely to occur in the dispersion stability and sensitivity of the near-infrared absorbing composition even after storage over time.

[0179] The method for controlling the water content is not particularly limited, and a known method can be used. For example, a method for producing a near-infrared absorbing composition while blowing in a dry inert gas, or a method for dehydrating the composition by adding molecular sieves after production, etc. are included. Among these, the method for producing the near-infrared absorbing composition while blowing in a dry inert gas is preferred.

[0180] The water content can be measured by a known method such as the Karl Fischer method.

[0181] <Amount of N-methylpyrrolidone in the near-infrared absorbing composition> The near-infrared absorbing composition of the present invention may contain N-methylpyrrolidone for various reasons, such as its use as a reaction solvent during the synthesis of the compound of the present invention. When N-methylpyrrolidone is contained, the content of N-methylpyrrolidone is preferably 1 to 2000 ppm by mass relative to the entire near-infrared absorbing composition. The upper limit of the content of N-methylpyrrolidone is preferably 1000 ppm by mass or less, more preferably 800 ppm by mass or less, and even more preferably 700 ppm by mass or less. The lower limit is preferably 10 ppm by mass or more, and more preferably 50 ppm by mass or more.

[0182] <Application> The near-infrared absorbing composition of the present invention can be used, for example, in the following applications.

[0183] (optical filter) The optical filter of the present invention is characterized by having a coating formed from the near-infrared absorbing composition of the present invention. The optical filter of the present invention includes a near-infrared cut filter and a near-infrared transmission filter. The near-infrared cut filter is mainly composed of a near-infrared absorbing dye and has the role of blocking near-infrared light and transmitting visible light. On the other hand, the near-infrared transmission filter is composed of a dye that absorbs visible light in addition to the near-infrared absorbing dye and has the role of blocking visible light and near-infrared light in the wavelength range absorbed by the near-infrared absorbing dye and transmitting near-infrared light with longer wavelengths.

[0184] [Near-infrared cut filter] Near-infrared cut filters are used for the following purposes, for example.

[0185] <<Digital Camera>> When capturing an image, a digital camera separates the received light into red, green, and blue filters and transmits the separated light to a photodiode, which converts the light into an electrical signal, thereby recognizing color. However, photodiodes also react to near-infrared light and convert it into an electrical signal, so a near-infrared cut filter can be used to block this. It is important that a filter that blocks near-infrared light has low absorption in the visible range. If the filter has high absorption in the visible range, the received light will be colored, adversely affecting the color recognition by the photodiode. The near-infrared absorbing dye of the present invention has low absorption in the visible range and is highly invisible, so it has little adverse effect on the color recognition by the photodiode.

[0186] <<Biometric authentication sensor>> Smartphones, tablet computers, bank ATMs, multimedia terminals, etc. For security purposes, devices are equipped with biometric authentication functions such as fingerprint authentication and finger vein authentication. Fingerprint authentication technology used in smartphones and tablet PCs in particular has been developing rapidly, and as photodiodes have been replaced by organic ones, the authentication range has expanded to the screen size (full screen), and fingerprint authentication sensors built into displays such as organic light-emitting diode (EL) displays and liquid crystal displays have been developed.

[0187] However, most fingerprint sensors built into displays use an optical system in which various light sources installed inside the display are shone onto the fingerprint and the reflected light is sensed. This means that when external illicit light (such as sunlight or LED lighting, which has a wide range of wavelengths and is strong) enters the sensor, it causes noise in the image capture, which makes the accuracy somewhat uncertain for outdoor use. The same is true for finger vein authentication used in bank ATMs and multimedia terminals; in stores with strong lighting or good sunlight, measures such as using covers to block external light are taken.

[0188] The near-infrared cut filter is effective in addressing these issues by absorbing and preventing external unauthorized light from reaching the sensor.

[0189] For example, when the optical filter is set on the front panel of a smartphone or tablet PC, it is necessary to have a design that is also attractive, and the optical filter of the present invention has the advantage of being suitable for use because it has no absorption in the visible region and is therefore invisible, i.e., highly transparent. Furthermore, the near-infrared absorbing composition of the present invention has excellent heat resistance, and therefore can be preferably used in terms of the process for producing a sensor, or a touch sensor or touch panel incorporating the sensor.

[0190] Furthermore, the external light that becomes noise in biometric authentication applications is light in the 650nm to 1000nm range that passes through living organisms, and since light in the 650nm to 800nm ​​range in particular is abundant in living spaces, cutting out light in this wavelength range will further increase the accuracy of biometric authentication.By combining blue or green dyes that absorb light in the 650nm to 700nm range with near-infrared absorbing dyes, invisibility will decrease, but the accuracy of biometric authentication can be further increased.

[0191] Examples of blue pigments include CI Pigment Blue 15:6, CI Pigment Blue 15:3, and CI Pigment Blue 15:1. Examples of green pigments include CI Pigment Green 7, CI Pigment Green 36, CI Pigment Green 58, CI Pigment Green 59, CI Pigment Green 62, and CI Pigment Green 63.

[0192] <<Display>> Near-infrared cut filters can also be incorporated into displays. A specific example is a liquid crystal display with a touch panel function, such as an electronic whiteboard. This liquid crystal display with a touch panel function has three functions: display, writing, and saving. The built-in touch panel also uses an optical method such as an infrared scanning method or an infrared projection method, and noise caused by external light, as mentioned above, has been a problem. Liquid crystal displays with a touch panel function are often used in schools, so accuracy and good response to touch are important. Incorporating the optical filter of the present invention into a display is preferable because it can cut out external light that causes noise. The optical filter of the present invention can also be preferably used as an anti-reflection film for various displays using liquid crystal, organic electroluminescence (EL), mini-LED, and micro-LED. By suppressing the reflection of not only visible light but also light in the near-infrared region, it has the advantage of being able to make black displays even darker. Because the near-infrared absorbing composition of the present invention has excellent heat resistance, it can also be preferably used in the resistance required for processes in display manufacturing.

[0193] [Near-infrared transmission filter] LEDs with wavelengths such as 850nm, 900nm, and 940nm are becoming widespread and are used for distance measurement in autonomous driving, biometric authentication (fingerprint authentication, iris authentication, face authentication, vein authentication, etc., or a combination of these), and light detection in various sensors. However, since light of all wavelengths, including ultraviolet light, visible light, and near-infrared light, is present in the atmosphere, filters are needed to block light of wavelengths other than those to be detected. By combining a near-infrared absorbing dye with a dye that absorbs visible light, an ultraviolet absorber, etc., it is possible to transmit only light with wavelengths longer than the absorption wavelength of the near-infrared absorbing dye, and block light with wavelengths shorter than that. Specifically, it is preferable to combine the near-infrared absorbing dye of the present invention with a blue dye, a yellow dye, a red dye, or a purple dye. For coating For applications involving molding, it is preferable to use CI Pigment Blue 15:3 or CI Pigment Blue 15:6 as the blue pigment, CI Pigment Yellow 139 as the yellow pigment, CI Pigment Red 254, CI Acid Red 52 or CI Acid Red 289 as the red pigment, and CI Pigment Violet 23 as the purple pigment. For applications involving molding, it is preferable to use CI Pigment Blue 15:3 or CI Pigment Blue 15:6 as the blue pigment, CI Pigment Yellow 147 as the yellow pigment, and CI Solvent Red 52 as the red pigment.

[0194] [Optical filter manufacturing method] The optical filter of the present invention can be manufactured by a printing method or a photolithography method. The formation of filter segments by a printing method allows for patterning by printing and drying a near-infrared absorbing composition, making this filter manufacturing method low-cost and suitable for mass production. Furthermore, advances in printing technology have made it possible to print fine patterns with high dimensional accuracy and smoothness. For printing, it is preferable to use a composition that prevents the ink from drying or solidifying on the printing plate or blanket. Controlling the fluidity of the ink on the printing press is also important, and the ink viscosity can be adjusted using a dispersant or extender pigment.

[0195] When forming filter segments by photolithography, a near-infrared absorbing composition prepared as a solvent-developable or alkali-developable resist material is applied to a substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating to a dry film thickness of 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern, which is placed in contact with or out of contact with the film. The film is then immersed in a solvent or alkali developer or sprayed with a developer to remove the uncured portions and form the desired pattern. The same process can then be repeated for other colors to produce filters. Furthermore, heating can be performed as needed to promote polymerization of the resist material. Photolithography can produce filters with higher precision than the printing method described above.

[0196] The substrate is not particularly limited, and a transparent substrate in the form of a sheet, film, or plate can be used. The color may be colorless or colored, and is not particularly limited. Examples of materials for the transparent substrate include highly transparent materials, such as polyester resins such as polyethylene terephthalate (PET) and polyethylene naphthalate (PEN), triacetyl cellulose (TAC), acrylic resins such as methyl methacrylate copolymers, styrene resins, polysulfone resins, polyethersulfone resins, polycarbonate resins, vinyl chloride resins, polymethacrylimide resins, and glass plates.

[0197] For development, an aqueous solution of sodium carbonate, sodium hydroxide, or the like is used as an alkaline developer, and organic alkalis such as dimethylbenzylamine and triethanolamine can also be used. An antifoaming agent or a surfactant can also be added to the developer. In order to increase the sensitivity to ultraviolet light exposure, after the resist material is coated and dried, a water-soluble or alkaline water-soluble resin, such as polyvinyl alcohol or a water-soluble acrylic resin, is coated and dried to inhibit polymerization by oxygen. After forming the film to prevent damage, ultraviolet exposure can also be carried out.

[0198] The optical filter of the present invention can also be produced by the electrodeposition method, transfer method, ink jet method, etc. in addition to the above method.

[0199] (molding application) The near-infrared absorbing dye of the present invention can also be used in molding applications, which are applications for producing films or three-dimensional objects by methods other than coating. When the near-infrared absorbing composition is used for molding purposes, it is preferably a melt-kneaded mixture of a near-infrared absorbing dye and a thermoplastic resin.

[0200] [Thermoplastic resin] Examples of the thermoplastic resin contained in the near-infrared absorbing composition for molding include polyolefin resin, acrylic resin, polystyrene resin, polyester resin, polyamide resin, polycarbonate resin, cycloolefin resin, and polyetherimide resin.

[0201] <<Polyamide resin>> The polyamide resin is a crystalline resin, and can be synthesized, for example, by a dehydration condensation reaction between a carboxylic acid component and a compound (Am) having two or more amino groups.

[0202] Examples of the carboxylic acid component include adipic acid, sebacic acid, isophthalic acid, terephthalic acid, etc. The carboxylic acid component may be a compound having three or more carboxyl groups. The compound (Am) having two or more amino groups may be, for example, a known compound, and examples thereof include aliphatic polyamines such as ethylenediamine, propylenediamine, trimethylenediamine, tetramethylenediamine, pentamethylenediamine, hexamethylenediamine, and triethylenetetramine; aliphatic polyamines including alicyclic polyamines such as isophoronediamine and dicyclohexylmethane-4,4'-diamine; aromatic polyamines such as phenylenediamine and xylylenediamine; and diaminoalcohols such as 1,3-diamino-2-propanol, 1,4-diamino-2-butanol, 1-amino-3-(aminomethyl)-3,5,5-trimethylcyclohexane-1-ol, 4-(2-aminoethyl)-4,7,10-triazadecan-2-ol, and 3-(2-hydroxypropyl)-o-xylene-α,α'-diamine. Commercially available polyamide resins include, for example, nylon 6 (manufactured by Toray Industries, Inc.), nylon 66 (manufactured by Toray Industries, Inc.), nylon 610, and the like.

[0203] <<Polycarbonate resin>> Polycarbonate resins are amorphous resins that are synthesized by reacting an aromatic dihydroxy compound with a carbonate precursor such as phosgene or a carbonate diester. In the case of a synthesis reaction using phosgene, for example, an interfacial method is preferred. In the case of a synthesis reaction using a carbonate diester, a transesterification method in which the reaction is carried out in a molten state is preferred.

[0204] Examples of aromatic dihydroxy compounds include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)octane, bis(4-hydroxyphenyl)phenylmethane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 1,1-bis(4-hydroxy-3-t-butylphenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, and 2,2-bis(4-hydroxy-3,5-dichlorophenyl). bis(hydroxyaryl)alkanes such as 1,1-bis(4-hydroxyphenyl)propane, bis(hydroxyaryl)cycloalkanes such as 1,1-bis(4-hydroxyphenyl)cyclopentane and 1,1-bis(4-hydroxyphenyl)cyclohexane, dihydroxydiaryl ethers such as 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxy-3,3'-dimethyldiphenyl ether, dihydroxydiaryl sulfides such as 4,4'-dihydroxydiphenyl sulfide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfide, dihydroxydiaryl sulfoxides such as 4,4'-dihydroxydiphenyl sulfoxide and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfoxide, and dihydroxydiaryl sulfones such as 4,4'-dihydroxydiphenyl sulfone and 4,4'-dihydroxy-3,3'-dimethyldiphenyl sulfone. Also, piperazine, dipiperidylhydroquinone, resorcinol, and 4,4'-dihydroxydiphenyls may be used in combination.

[0205] Examples of the carbonate precursor include phosgene, diaryl carbonates such as diphenyl carbonate and ditolyl carbonate, and dialkyl carbonates such as dimethyl carbonate and diethyl carbonate.

[0206] The viscosity average molecular weight of the polycarbonate resin is preferably 15,000 to 30,000, and more preferably 16,000 to 27,000. The viscosity average molecular weight in this specification is a value converted from the solution viscosity measured at 25°C using methylene chloride as a solvent.

[0207] Commercially available polycarbonate resins include Iupilon H-4000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity average molecular weight 16,000), Iupilon S-3000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity average molecular weight 23,000), and Iupilon E-2000 (manufactured by Mitsubishi Engineering Plastics Corporation, viscosity average molecular weight 27,000).

[0208] <<Cycloolefin resin>> Cycloolefin resins are amorphous resins with alicyclic structures in the main chain and / or side chain. Examples of alicyclic structures include norbornene polymers, monocyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrogenated versions of these. Among these, norbornene polymers are preferred due to their excellent moldability and transparency. Examples of norbornene monomers include bicyclo[2.2.1]hept-2-ene (common name: norbornene), tricyclo[4.3.0.12,5]deca-3,7-diene (common name: dicyclopentadiene), 7,8-benzotricyclo[4.3.0.12,5]dec-3-ene (common name: methanotetrahydrofluorene), and tetracyclo[4.4.0.12,5.17,10]dodec-3-ene (common name: tetracyclododecene). Commercially available cycloolefin resins include, for example, Topas (manufactured by Polyplastics Co., Ltd.) and Apel (manufactured by Mitsui Chemicals, Inc.).

[0209] <<Polyetherimide resin>> Polyetherimide resins are amorphous resins with a glass transition temperature above 180°C, and have good transparency, high strength, high heat resistance, high modulus of elasticity, and broad chemical resistance, which is why they are widely used in a variety of applications, including automotive, telecommunications, aerospace, electrical / electronics, transportation, and healthcare. One process for producing polyetherimide resins is by polymerization of alkali metal salts of dihydroxy aromatic compounds, such as bisphenol A disodium salt (BPA·Na2), with bis(halophthalimide). The molecular weight of the resulting polyetherimide resin can be determined in two ways: The polymerization rate can be controlled by various methods. The first method is to use a molar excess of the bis(halophthalimide) relative to the alkali metal salt of the dihydroxyaromatic compound. The second method is to prepare the bis(halophthalic anhydride) in the presence of a monofunctional compound, such as phthalic anhydride, which forms the end-capping agent. The phthalic anhydride reacts with a portion of the organic diamine to form the monohalo-bis(phthalimide). The monohalo-bis(phthalimide) serves as the end-capping agent in the polymerization step by reaction with the phenoxide end groups on the growing polymer chain. Commercially available polyetherimide resins include ULTEM (manufactured by Saudi Basic Industries Corporation).

[0210] The thermoplastic resin is preferably a crystalline resin having a melting point of 100 to 500° C. or an amorphous resin having a glass transition temperature of 60 to 300° C. Both the melting point and the glass transition temperature can be measured using a differential scanning calorimeter, a thermogravimetric differential thermal analyzer, or the like.

[0211] The near-infrared absorbing composition for molding may contain additives other than the near-infrared absorbing dye and the thermoplastic resin. Examples of the additives include an ultraviolet absorber, a light stabilizer, an antioxidant, a colorant, a dispersant, etc. These additives are compounds known in the art for use in molded articles.

[0212] The ultraviolet absorber is used to impart ultraviolet resistance to the molded article. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, triazine-based, and salicylic acid ester-based ultraviolet absorbers. The content of the ultraviolet absorber is preferably 0.01 to 5% by mass based on 100% by mass of the composition.

[0213] The light stabilizer is used to impart UV resistance to the molded article, and is preferably used in combination with a UV absorber. A preferred example of the light stabilizer is a hindered amine light stabilizer. The content of the light stabilizer is preferably 0.01 to 5% by mass relative to 100% by mass of the composition.

[0214] Antioxidants are used to reduce deterioration of molded articles when exposed to high temperatures due to exposure to natural or artificial light sources. Examples of preferred antioxidants include monophenols, bisphenols, polymeric phenols, sulfur-based, and phosphoric acid-based antioxidants. The content of the antioxidant is preferably 0.01 to 5% by mass based on 100% by mass of the composition.

[0215] The dispersant is used to disperse the near-infrared absorbing pigment more uniformly in the molded article. Examples of the dispersant include polyolefin wax, fatty acid wax, fatty acid ester wax, partially saponified fatty acid ester wax, and saponified fatty acid wax. The content of the dispersant is preferably 50 to 250% by mass relative to 100% by mass of the near-infrared absorbing pigment.

[0216] [Preparation of near-infrared absorbing composition for molding] The near-infrared absorbing composition for molding can be produced by melt-kneading a near-infrared absorbing dye and a thermoplastic resin. The melt-kneading temperature varies depending on the resin, but is preferably 230°C or higher, more preferably 270°C or higher. After melt-kneading, it is preferable to cool the mixture. The upper limit of the melt-kneading temperature is not limited, as it varies depending on the type of thermoplastic resin. The upper limit is preferably 500°C or lower, more preferably 450°C or lower. Furthermore, the upper limit must be lower than the sublimation temperature or decomposition temperature of the near-infrared absorbing pigment of the present invention.

[0217] Examples of the melt kneading device include a single-screw kneading extruder, a twin-screw kneading extruder, and a tandem twin-screw kneading extruder.

[0218] The resin composition is preferably prepared as a so-called masterbatch. The masterbatch is then melt-kneaded with a diluting resin (thermoplastic resin) to prepare a molded body. In comparison with a molded product produced without using a masterbatch, the near-infrared absorbing dye of the present invention can be more easily dispersed uniformly in the molded product, and aggregation of the near-infrared absorbing dye can be suppressed. This improves the transparency of the molded product. In producing the masterbatch, it is preferable to form the near-infrared absorbing dye into pellets using a pelletizer after the melt-kneading. When prepared as a masterbatch, the content of the near-infrared absorbing dye is preferably 0.01 to 20% by mass, and more preferably 0.05 to 2% by mass, based on 100% by mass of the composition.

[0219] (Optical recording media) The near-infrared absorbing composition of the present invention can be used as an optical recording medium. When a film or molded article formed from the near-infrared absorbing composition is irradiated with near-infrared rays, the crystalline state of the dye changes, causing a change in the refractive index of the film or molded article. This principle is used in recording media such as optical disks.

[0220] (Laser welding materials and laser marking materials) The near-infrared absorbing composition of the present invention can be used as a laser welding material or laser marking material. When a coating or molded article formed from the near-infrared absorbing composition is irradiated with a laser having a wavelength absorbed by the near-infrared absorbing dye, the dye absorbs the laser light and generates heat, causing the resin to melt and carbonize. When melted, the resin can be welded to other resins, making marking possible. [Example]

[0221] The present invention will be described below based on examples, but the present invention is not limited thereto. In the examples and comparative examples, "parts" means "parts by mass." Furthermore, "PGMAC" means propylene glycol monomethyl ether acetate.

[0222] (Method for identifying compounds) The compounds used in the present invention were identified by infrared absorption spectroscopy and MALDI TOF-MS spectroscopy. The MALDI TOF-MS spectroscopy was performed using a Bruker Daltonics MALDI mass spectrometer, Autoflex III, and the positive mode of the spectroscopy was The compounds were identified by the agreement of the molecular ion peaks in the mass spectrum with the calculated mass numbers. The compositions were determined by calculating the relative intensities of each molecular ion peak relative to the sum of all molecular ion peak intensities in the mass spectrum, and the ratio of these relative intensities was considered to be the molar ratio. Infrared absorption spectra were measured using a Nicolet is5 FT / IR-410 (Thermo Fisher Scientific) at a resolution of 2 cm using the ATR method. Regarding the compounds of the present invention, a compound represented by general formula (1) is referred to as a dimer, a compound represented by general formula (2) as a trimer, and a compound represented by general formula (4) as a tetramer.

[0223] (Method for measuring water content of near-infrared absorbing composition) The water content (mg) was measured using a Karl Fischer titrator (volumetric titration water content measuring device KF-06 manufactured by Mitsubishi Chemical Corporation), and the water content (%) was calculated using the following formula. Moisture content (%) = [moisture content (mg) / measured sample weight (mg)] x 100

[0224] (Method for measuring specific metal atoms in near-infrared absorbing composition) The amount of specific metal atoms in the near-infrared absorbing composition was measured by drying the near-infrared absorbing composition at 180°C, decomposing the powder using microwaves, and then using an ICP optical emission spectrometer Varian 720-ES manufactured by Agilent Technologies.

[0225] (Acid value of resin-type dispersant and binder resin) The acid value of the resin-type dispersant and binder resin is measured by 0.1N potassium hydroxide in ethanol. The acid value of the resin-type dispersant and binder resin indicates the acid value of the nonvolatile content.

[0226] (Weight average molecular weight (Mw) of acidic resin-type dispersant and binder resin) The weight-average molecular weight (Mw) of the acidic resin-type dispersant and binder resin is the polystyrene-equivalent weight-average molecular weight (Mw) measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, using THF as the developing solvent.

[0227] (Weight average molecular weight (Mw) of basic resin-type dispersant) The weight-average molecular weight (Mw) of the basic resin-type dispersant is the weight-average molecular weight (Mw) in terms of polystyrene measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, using a solution of 3 mM triethylamine and 10 mM LiBr in N,N-dimethylformamide as the developing solvent.

[0228] (Amine value of resin-type dispersant) The amine value of the resin-type dispersant was determined by potentiometric titration using a 0.1N hydrochloric acid solution, and then converted into the potassium hydroxide equivalent. The amine value of the resin-type dispersant indicates the amine value of the non-volatile content.

[0229] (Quaternary ammonium salt value of resin-type dispersant) The quaternary ammonium salt value of the resin-type dispersant was determined by titration with 0.1N silver nitrate aqueous solution using 5% potassium chromate aqueous solution as an indicator, and then converted into the potassium hydroxide equivalent. The quaternary ammonium salt value of the resin-type dispersant below indicates the quaternary ammonium salt value of the non-volatile content.

[0230] [Example 1] (Production of Compound (a)) In a reaction vessel, 10.7 parts of aniline, 120 parts of bromobenzene, and 25.7 parts of diazabicyclooctane were added and stirred. Then, 95.2 parts of a 1 mol / L toluene solution of titanium tetrachloride was added dropwise. After the dropwise addition, 10.0 parts of indigo was added and refluxed for 10 hours. After the reaction was completed, methanol was added and the mixture was filtered to obtain a green powder. This was separated with dichloromethane and water, and the organic layer was concentrated to obtain 14.6 parts of compound (1).

[0231] [Compound (1)] [ka]

[0232] In a reaction vessel, 13.5 parts of compound (1), bis(2,4-pentanedionato)zinc(II 9.0 parts of tetrahydrofuran were mixed and stirred, and the mixture was heated to 40°C and stirred for 5 hours. The reaction solution was cooled to 30°C while stirring, and then poured into 500 parts of methanol with stirring to obtain a blue slurry. This slurry was filtered, washed with 500 parts of methanol, then with 500 parts of water, and dried to obtain 12.2 parts of compound (a). Mass analysis by TOF-MS confirmed that the molecular ion peak in the obtained mass spectrum matched the calculated mass number, identifying the compound. The main component of compound (a) was compound (a-1), and the formation of compound (a-2) (hereinafter referred to as trimer) and compound (a-3) (hereinafter referred to as tetramer) was also confirmed by TOF-MS. The infrared absorption spectrum of compound (a) is shown in Figure 1.

[0233] [ka]

[0234] [Example 2] (Production of Compound (b)) The same procedure as in the synthesis of compound (a) was carried out, except that the amount of bis(2,4-pentanedionato)zinc(II) used in the synthesis of compound (a) was changed from 9.0 parts to 25.0 parts, to obtain 11.7 parts of compound (b). As a result of mass analysis by TOF-MS, the mass spectrum obtained was The compound was identified based on the agreement between the molecular ion peak and the calculated mass number. The main component of compound (b) was compound (a-2). The infrared absorption spectrum of compound (b) is shown in Figure 2.

[0235] [Example 3] (Production of Compound (c)) In a reaction vessel, 13.5 parts of compound (1), 15.0 parts of zinc acetate dihydrate, and 120 parts of N-methylpyrrolidone were mixed and stirred. The mixture was heated to 60°C and then stirred for 5 hours. The reaction solution was cooled to 30°C while stirring, and then poured into 500 parts of methanol with stirring to obtain a blue slurry. This slurry was filtered, washed with 500 parts of methanol, then with 500 parts of water, and dried to obtain 12.3 parts of compound (c). Mass analysis by TOF-MS confirmed that the molecular ion peak in the mass spectrum matched the calculated mass number, confirming the identity of the compound. The main component of compound (c) was compound (a-1). The infrared absorption spectrum of compound (c) is shown in Figure 3.

[0236] [Example 4] (Production of Compound (d)) The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 18.5 parts of 2,3-dichloroaniline, to obtain 17.8 parts of compound (2).

[0237] [Compound (2)] [ka]

[0238] The same procedure as in the synthesis of compound (b) was performed, except that 13.5 parts of compound (1) used in the synthesis of compound (b) was replaced with 15.8 parts of compound (2), to obtain 14.6 parts of compound (d). As a result of mass analysis by TOF-MS, the molecular ion peak in the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of compound (d) was compound (d-1). The infrared absorption spectrum of compound (d) is shown in Figure 4.

[0239] Compound (d-1) [ka]

[0240] [Example 5] (Production of Compound (e)) The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 14.6 parts of 3,4-difluoroaniline, to obtain 16.2 parts of compound (3).

[0241] [Compound (3)] [ka]

[0242] The same procedure as in the synthesis of compound (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of compound (b) was changed to 14.7 parts of compound (3), and 13.4 parts of compound (e) was obtained. As a result of mass analysis by TOF-MS, the molecular ion peak in the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of compound (e) was compound (e-1). The infrared absorption spectrum of compound (e) is shown in Figure 5.

[0243] Compound (e-1) [ka]

[0244] [Example 6] (Production of compound (f)) The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 19.8 parts of 4-bromoaniline, to obtain 20.0 parts of compound (4).

[0245] [Compound (4)] [ka]

[0246] The same procedure as in the synthesis of compound (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of compound (b) was replaced with 19.7 parts of compound (4), to obtain 15.0 parts of compound (f). As a result of mass analysis by TOF-MS, the molecular ion peak in the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of compound (f) was compound (f-1).

[0247] Compound (f-1) [ka]

[0248] [Example 7] (Production of compound (g)) The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 12.3 parts of p-toluidine, to obtain 14.9 parts of compound (5).

[0249] [Compound (5)] [ka]

[0250] The same procedure as in the synthesis of compound (b) was performed, except that 13.5 parts of compound (1) used in the synthesis of compound (b) was replaced with 14.0 parts of compound (5), to obtain 13.2 parts of compound (g). As a result of mass analysis by TOF-MS, the molecular ion peak in the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of compound (g) was compound (g-1).

[0251] Compound (g-1) [ka]

[0252] [Example 8] (Production of compound (h)) The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 16.0 parts of 4-(methylthio)aniline, to obtain 16.4 parts of compound (6).

[0253] [Compound (6)] [ka]

[0254] The same procedure as in the synthesis of compound (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of compound (b) was replaced with 15.0 parts of compound (6), to obtain 14.2 parts of compound (h). As a result of mass analysis by TOF-MS, the molecular ion peak in the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of compound (h) was compound (h-1).

[0255] Compound (h-1) [ka]

[0256] [Example 9] (Production of Compound (i)) The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 20.0 parts of sulfanilic acid, to obtain 17.5 parts of compound (7).

[0257] [Compound (7)] [ka]

[0258] The same procedure as in the synthesis of compound (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of compound (b) was replaced with 16.0 parts of compound (6), to obtain 15.2 parts of compound (i). As a result of mass analysis by TOF-MS, the molecular ion peak in the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of compound (i) was compound (i-1).

[0259] Compound (i-1) [ka]

[0260] [Example 10] (Production of compound (j)) The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 14.2 parts of 4-amino-2-methylphenol, to obtain 17.5 parts of compound (8).

[0261] [Compound (8)] [ka]

[0262] The same procedure as in the synthesis of compound (b) was performed, except that 13.5 parts of compound (1) used in the synthesis of compound (b) was replaced with 14.5 parts of compound (8), to obtain 13.1 parts of compound (j). As a result of mass analysis by TOF-MS, the molecular ion peak in the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of compound (j) was compound (j-1).

[0263] Compound (j-1) [ka]

[0264] [Example 11] (Production of compound (k)) 10.7 parts of the aniline used in the synthesis of compound (1) was replaced with 14.2 parts of 3-methoxyaniline The same procedure as in the synthesis of compound (1) was carried out except for changing the above to obtain 17.3 parts of compound (9).

[0265] [Compound (9)] [ka]

[0266] The same procedure as in the synthesis of compound (b) was performed, except that 13.5 parts of compound (1) used in the synthesis of compound (b) was replaced with 14.5 parts of compound (9), to obtain 12.8 parts of compound (k). As a result of mass analysis by TOF-MS, the molecular ion peak in the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of compound (k) was compound (k-1).

[0267] Compound (k-1) [ka]

[0268] [Example 12] (Production of Compound (l)) The same procedure as in the synthesis of compound (1) was carried out, except that 10.7 parts of aniline used in the synthesis of compound (1) was changed to 21.3 parts of 4-phenoxyaniline, to obtain 18.8 parts of compound (10).

[0269] [Compound (10)] [ka]

[0270] The same procedure as in the synthesis of compound (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of compound (b) was replaced with 16.5 parts of compound (10), to obtain 15.3 parts of compound (l). As a result of mass analysis by TOF-MS, the molecular ion peak in the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of compound (l) was compound (l-1).

[0271] Compound (l-1) [ka]

[0272] [Example 13] (Production of Compound (m)) 10.7 parts of the aniline used in the synthesis of compound (1) was dissolved in N,N-diethyl-1,4-phenylene The same procedure as in the synthesis of compound (1) was carried out except that the amount of diamine was changed to 18.8 parts, to obtain 18.8 parts of compound (11).

[0273] [Compound (11)] [ka]

[0274] The same procedure as in the synthesis of compound (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of compound (b) was replaced with 15.7 parts of compound (11), to obtain 14.2 parts of compound (m). As a result of mass analysis by TOF-MS, the molecular ion peak in the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of compound (m) was compound (m-1).

[0275] Compound (m-1) [ka]

[0276] [Example 14] (Production of Compound (n)) 10.7 parts of the aniline used in the synthesis of compound (1) was mixed with 13.7 parts of 4-cyanoaniline. The same procedure as in the synthesis of compound (1) was carried out except for the above change, to obtain 16.0 parts of compound (12).

[0277] [Compound (12)] [ka]

[0278] The same procedure as in the synthesis of compound (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of compound (b) was replaced with 15.2 parts of compound (12), to obtain 14.6 parts of compound (n). As a result of mass analysis by TOF-MS, the molecular ion peak in the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of compound (n) was compound (n-1).

[0279] Compound (n-1) [ka]

[0280] [Example 15] (Production of Compound (o)) The same procedure as in the synthesis of compound (1) was carried out, except that 10.0 parts of indigo used in the synthesis of compound (1) was changed to 16.0 parts of Vat Blue 35, to obtain 19.5 parts of compound (13).

[0281] [Compound (13)] [ka]

[0282] The same procedure as in the synthesis of compound (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of compound (b) was replaced with 18.7 parts of compound (13), to obtain 17.5 parts of compound (o). As a result of mass analysis by TOF-MS, the molecular ion peak in the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of compound (o) was compound (o-1).

[0283] Compound (o-1) [ka]

[0284] [Example 16] (Production of Compound (p)) The same procedure as in the synthesis of compound (1) was carried out, except that 10.0 parts of indigo used in the synthesis of compound (1) was changed to 22.0 parts of Vat Blue 5, to obtain 24.4 parts of compound (14).

[0285] [Compound (14)] [ka]

[0286] The same procedure as in the synthesis of compound (b) was carried out, except that 13.5 parts of compound (1) used in the synthesis of compound (b) was replaced with 23.9 parts of compound (14), to obtain 21.5 parts of compound (p). As a result of mass analysis by TOF-MS, the molecular ion peak in the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of compound (p) was compound (p-1).

[0287] Compound (p-1) [ka]

[0288] [Example 17] (Production of compound (q))

[0289] The same procedure as in the synthesis of compound (a) was repeated, except that 9.0 parts of bis(2,4-pentanedionato)zinc(II) used in the synthesis of compound (a) was replaced with 8.8 parts of bis(2,4-pentanedionato)nickel(II) hydrate, yielding 11.5 parts of compound (q). TOF-MS mass analysis revealed that the molecular ion peak in the mass spectrum matched the calculated mass number, identifying the compound. The main component of compound (q) was compound (q-1). The infrared absorption spectrum of compound (q) is shown in Figure 6.

[0290] Compound (q-1) [ka]

[0291] [Example 18] (Production of Compound (r))

[0292] Compound (c) was synthesized by the same procedure as in the synthesis of compound (c), except that 15.0 parts of zinc acetate dihydrate was replaced with 17.0 parts of nickel (II) acetate tetrahydrate. 10.1 parts of compound (r) were obtained. As a result of mass analysis by TOF-MS, the molecular ion peak in the obtained mass spectrum matched the mass number obtained by calculation, and the obtained compound was identified. The main component of compound (r) was compound (q-1).

[0293] [Example 19] (Production of Compound (s)) The same procedure as in the synthesis of compound (a) was performed, except that 9.0 parts of bis(2,4-pentanedionato)zinc(II) used in the synthesis of compound (a) was replaced with 12.6 parts of bis(2,4-pentanedionato)cobalt(II), yielding 12.7 parts of compound (s). TOF-MS mass analysis revealed that the molecular ion peak in the mass spectrum matched the calculated mass number, identifying the compound. The main component of compound (s) was compound (s-1). The infrared absorption spectrum of compound (s) is shown in Figure 7.

[0294] Compound (s-1) [ka]

[0295] [Comparative Example 1] (Synthesis of comparative compound (t)) According to JP 2012-224593 A, a comparative compound (t) having the following structure was obtained.

[0296] compound(t) [ka]

[0297] The composition of the resulting compound is shown in Table 1.

[0298] [Table 1]

[0299] <Method for producing binder resin solution> (Production of binder resin 1 solution) A separable four-necked flask equipped with a thermometer, condenser, nitrogen gas inlet, and stirrer was charged with 70.0 parts of cyclohexanone, heated to 80°C, and the atmosphere inside the reaction vessel was replaced with nitrogen. A mixture of 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 0.4 parts of 2,2'-azobisisobutyronitrile was added dropwise over two hours. After the addition was completed, the reaction was continued for another three hours, yielding a solution of acrylic resin with a weight average molecular weight (Mw) of 26,000. After cooling to room temperature, approximately 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monoethyl ether acetate was added to the resin solution synthesized earlier so that the non-volatile content was 20 mass % to prepare binder resin 1 solution.

[0300] (Production of binder resin 2 solution) A separable four-neck flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer was charged with 370 parts of cyclohexanone, and the temperature was raised to 80°C. The atmosphere in the flask was replaced with nitrogen, and then 18 parts of dicyclopentanyl methacrylate, 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2'- A mixture of 2.0 parts of azobisisobutyronitrile was added dropwise over 2 hours. After reacting for 3 hours at 100°C, a solution of 1.0 parts azobisisobutyronitrile in 50 parts cyclohexanone was added, and the reaction continued for another hour at 100°C. Next, the atmosphere in the vessel was purged with air, and 9.3 parts acrylic acid (100% of glycidyl groups), 0.5 parts trisdimethylaminophenol, and 0.1 parts hydroquinone were added to the vessel. The reaction continued for 6 hours at 120°C, and the reaction was terminated when the solids acid value reached 0.5, yielding an acrylic resin solution. Next, 19.5 parts tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts triethylamine were added, and the reaction continued for 3.5 hours at 120°C, yielding an acrylic resin solution. After cooling to room temperature, approximately 2 g of the resin solution was sampled and dried at 180°C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether acetate was added to the resin solution synthesized earlier to adjust the nonvolatile content to 20% by mass, to prepare binder resin 2 solution. The weight-average molecular weight (Mw) was 19,000.

[0301] (Production of binder resin 3 solutions) A separable four-neck flask was equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer. 207 parts of propylene glycol monomethyl ether acetate was charged into the reaction vessel, which was then heated to 80°C. The atmosphere inside the reaction vessel was replaced with nitrogen, and then a mixture of 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate ("Aronix (registered trademark) M110" manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile was added through the dropping tube. The mixture was added dropwise over two hours. After completion of the addition, the reaction was continued for another three hours to obtain a copolymer resin solution. The nitrogen gas supply was stopped and dry air was injected into the entire obtained copolymer solution for one hour while stirring. After cooling to room temperature, a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate ("KARENZ (registered trademark) MOI" manufactured by Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of propylene glycol monomethyl ether acetate was added dropwise at 70°C over three hours. After completion of the addition, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. Propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass to prepare binder resin 3 solution. The weight-average molecular weight (Mw) was 18,000.

[0302] <Method of manufacturing resin-type dispersant solution>

[0303] (Production of basic resin-type dispersant solution 1) A reaction vessel equipped with a stirrer and a thermometer was charged with 41 parts of N,N-dimethylpropanediamine and 120 parts of chloroform, and the mixture was stirred at room temperature, and 50 parts of methacrylic acid chloride was added dropwise over 1 hour. After stirring at room temperature for 3 hours, 1 After confirming the completion of the reaction by H-NMR, the reaction solution was washed successively with 300 parts of ion-exchanged water and 200 parts of saturated saline, and then 20 g of magnesium sulfate was added to the organic layer, stirred, and then filtered. The solvent in the resulting solution was distilled off using a rotary evaporator, and 58 parts of compound [B] represented by the following formula (5) was obtained as a pale yellow, transparent liquid (yield 85%). The resulting compound was identified as follows: 1 H-NMR was performed.

[0304] Formula (5) [ka]

[0305] A reaction vessel equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 15.7 parts of methyl methacrylate, 47.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine. The mixture was stirred at 50 ° C for 1 hour while flowing nitrogen, and the system was purged with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of propylene glycol monomethyl ether acetate (PGMAc) were charged, and the temperature was raised to 110 ° C under a nitrogen stream to initiate polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled and the solids content was measured. It was confirmed that the polymerization conversion rate was 98% or higher based on the nonvolatile content. Next, 25 parts of PGMAc and 30.3 parts of the above compound [B] as the second block monomer were added to the reaction vessel, and the reaction was continued with stirring while maintaining the temperature at 110°C under a nitrogen atmosphere. Two hours after adding the compound [B] represented by the above formula (5), a sample of the polymerization solution was taken and the solid content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more, calculated from the nonvolatile content. Further, 6.8 parts of benzyl chloride was added to the reactor, and the mixture was stirred for 3 hours while maintaining the temperature at 110°C under a nitrogen atmosphere, and then cooled. PGMAc was added to the block copolymer solution synthesized above to achieve a nonvolatile content of 40 wt%. In this way, a basic resin-type dispersant 1 solution was obtained with an amine value per solid of 70 mg KOH / g, a quaternary ammonium salt value of 30 mg KOH / g, a weight-average molecular weight (Mw) of 9,800, and a nonvolatile content of 40 wt%.

[0306] (Production of basic resin-type dispersant 2 solution) A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine. The mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to initiate polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured. Based on the nonvolatile content, it was confirmed that the polymerization conversion was 98% or higher. Next, 61 parts of PGMAc and 20 parts of dimethylaminoethyl methacrylate (DM) as the second block monomer were added to the reactor, and the reaction was continued with stirring while maintaining the temperature at 110°C under a nitrogen atmosphere. Two hours after adding the dimethylaminoethyl methacrylate, a sample of the polymerization solution was taken and the nonvolatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or higher based on the nonvolatile content, and the reaction solution was cooled to room temperature to terminate the polymerization. PGMAc was added to the block copolymer solution synthesized previously so that the nonvolatile content was 40% by mass. In this way, the amine value per nonvolatile content was 71.4 mg KOH / g, and the weight average A basic resin-type dispersant 2 solution having an average molecular weight of 9,900 (Mw) and a nonvolatile content of 40% by mass was obtained.

[0307] (Production of basic resin-type dispersant 3 solution) A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine. The mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to initiate polymerization of the first block. After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured. Based on the nonvolatile content, it was confirmed that the polymerization conversion was 98% or higher. Next, 61 parts of PGMAc and 25.6 parts of an aqueous solution of methacryloyloxyethyltrimethylammonium chloride ("Acryester DMC78" manufactured by Mitsubishi Rayon Co., Ltd.) as the second block monomer were added to the reactor, and the reaction was continued with stirring while maintaining the temperature at 110°C under a nitrogen atmosphere. Two hours after adding the methacryloyloxyethyltrimethylammonium chloride, a sample of the polymerization solution was taken and the nonvolatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or higher based on the nonvolatile content, and the reaction solution was cooled to room temperature to terminate the polymerization. PGMAc was added to the block copolymer solution synthesized above so that the nonvolatile content was 40% by mass. In this way, a basic resin-type dispersant 3 solution was obtained with an amine value per nonvolatile content of 29.4 mg KOH / g, a weight-average molecular weight of 9,800 (Mw), and a nonvolatile content of 40% by mass.

[0308] (Production of 4 acidic resin-type dispersant solutions) A reaction vessel equipped with a gas inlet tube, thermostat, condenser, and stirrer was charged with 10 parts methacrylic acid, 90 parts methyl methacrylate, 50 parts ethyl acrylate, 50 parts tert-butyl acrylate, and 50 parts propylene glycol monomethyl ether acetate, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 50°C with stirring, and 12 parts 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts 2,2'-azobisisobutyronitrile in 90 parts propylene glycol monomethyl ether acetate was added while the reaction was continued for 7 hours. Solid content measurement confirmed that 95% reaction had occurred. 19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out for 7 hours at 100°C. After confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, the reaction was terminated, and propylene glycol monomethyl ether acetate was added to dilute the solution to a solids content of 40% by measuring the solids content, yielding a solution of acidic resin-type dispersant 4 with an acid value of 70 mgKOH / g and a weight-average molecular weight of 8500 (Mw).

[0309] (Production of resin-type dispersant 5 solution) DISPER-BYK111 (manufactured by BYK Japan; acid value 129 mg KOH / g (solid content 95%) was diluted in the same manner as in Resin Type Dispersant 1 Solution to prepare Resin Type Dispersant 5 Solution.

[0310] (Production of basic resin-type dispersant 6 solution) A reactor equipped with a gas inlet tube, thermostat, condenser, and stirrer was charged with 40.0 parts t-butyl acrylate, 5.0 parts methacrylic acid, 30.0 parts methyl methacrylate, and 1.6 parts tetramethylethylenediamine, and then purged with nitrogen gas. The reactor was heated to 50°C with stirring, and 2.1 parts ethyl bromoisobutyrate, 1.9 parts cuprous chloride, and 62.3 parts propylene glycol monomethyl ether were added. The temperature was raised to 100°C to initiate polymerization of the first block. After 4 hours of polymerization, a sample was taken of the polymerization solution and the solids content was measured. Based on the nonvolatile content, the polymerization conversion was confirmed to be 98% or higher. Next, 8.1 parts propylene glycol monomethyl ether and 25.0 parts dimethylaminoethyl methacrylate methyl chloride salt (second block monomer) were added to the reactor, and the reaction was continued under a nitrogen atmosphere at 100°C with stirring. Two hours after adding the dimethylaminoethyl methacrylate methyl chloride salt, the polymerization solution was sampled and the solids content was measured. The polymerization conversion rate of the second block was confirmed to be 98% or higher, calculated from the nonvolatile content. The reaction solution was cooled to room temperature to terminate the polymerization. The solution was diluted with propylene glycol monomethyl ether acetate to a solids content of 40%, yielding a solution of basic resin-type dispersant 6 with a quaternary ammonium salt value of 67 mg KOH / g and a weight-average molecular weight (Mw) of 9,200.

[0311] <Production of near-infrared absorbing composition> [Example 20] (Near infrared absorbing composition (D-1)) A mixture of the following composition was stirred and mixed uniformly, then dispersed in an Eiger mill using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter to prepare a near-infrared absorbing composition. Compound (a): 10.0 parts Resin-type dispersant solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47.5 parts The near infrared absorbing composition (D-1) had a water content of 1.1% and a total amount of specific metal atoms of 180 ppm based on the total amount of the near infrared absorbing composition (D-1).

[0312] [Example 21] (Near infrared absorbing composition (D-2)) A mixture of the following composition was stirred and mixed uniformly, then dispersed in an Eiger mill using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter to prepare a near-infrared absorbing composition. Compound (a): 10.0 parts Resin-type dispersant solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 46.5 parts Ion-exchanged water: 1.0 parts The near infrared absorbing composition (D-2) had a water content of 2.2% and a total amount of specific metal atoms of 185 ppm based on the total amount of the near infrared absorbing composition (D-2).

[0313] [Example 22] (Near infrared absorbing composition (D-3)) Molecular sieves were added to the near-infrared absorbing composition (D-1), and the mixture was left to stand for 24 hours, and then filtered to obtain a near-infrared absorbing composition (D-3). The near infrared absorbing composition (D-3) had a water content of 0.1% and a total amount of specific metal atoms of 177 ppm based on the total amount of the near infrared absorbing composition (D-3).

[0314] <Purification of compound (a) 1> 15.0 parts of compound (a) and 1000 parts of ion-exchanged water were placed in a beaker and heated to 60°C for 1 The mixture was heated and stirred for 1 hour, filtered, washed with 2000 parts of ion-exchanged water, and dried.

[0315] <Purification of compound (a) 2> 15.0 parts of compound (a) and 1000 parts of methanol were placed in a beaker and left at room temperature for 1 hour. The mixture was stirred, filtered, washed with 500 parts of methanol and 2000 parts of ion-exchanged water, and then dried.

[0316] <Purification of compound (a) 3> In the synthesis of compound (a), the procedure of washing with 500 parts of methanol, followed by washing with 500 parts of water, was repeated, except that washing with 100 parts of water was performed instead of washing with methanol, instead of washing with 500 parts of water.

[0317] [Example 23] (Near infrared absorbing composition (D-4)) A near-infrared absorbing composition (D-4) was prepared in the same manner as the near-infrared absorbing composition (D-1), except that the compound (a) was changed to the compound obtained in purification 1 of the compound (a). The near infrared absorbing composition (D-4) had a water content of 1.0% and a total amount of specific metal atoms of 100 ppm based on the total amount of the near infrared absorbing composition (D-4).

[0318] [Example 24] (Near infrared absorbing composition (D-5)) A near-infrared absorbing composition (D-5) was prepared in the same manner as the near-infrared absorbing composition (D-1), except that the compound (a) was changed to the compound obtained in purification 2 of the compound (a). The near infrared absorbing composition (D-5) had a water content of 0.9% and a total amount of specific metal atoms of 50 ppm based on the total amount of the near infrared absorbing composition (D-5).

[0319] [Example 25] (Near infrared absorbing composition (D-6)) A near-infrared absorbing composition (D-6) was prepared in the same manner as the near-infrared absorbing composition (D-1), except that the compound (a) was changed to the compound obtained in purification 3 of the compound (a). The near infrared absorbing composition (D-6) had a water content of 1.2% and a total amount of specific metal atoms of 1050 ppm based on the total amount of the near infrared absorbing composition (D-6).

[0320] [Examples 26 to 64, Comparative Example 2] (Near infrared absorbing compositions (D-7) to (D-45), (D-84)) Hereinafter, near infrared absorbing compositions (D-7) to (D-45) and (D-84) were prepared in the same manner as for the near infrared absorbing composition (D-1), except that the compositions and amounts of the compounds, resin-type dispersant solution, binder resin solution and PGMAc were changed to those shown in Table 2.

[0321] [Example 65] (Near infrared absorbing composition (D-46)) A mixture of the following composition was stirred and mixed uniformly, then dispersed in an Eiger mill using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter to prepare a near-infrared absorbing composition. Compound (b): 7.0 parts Other near-infrared absorbing dye (X-1): 3.0 parts Resin-type dispersant 1 solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47.5 parts

[0322] [Examples 66 to 102] (Near infrared absorbing compositions (D-47) to (D-83)) Hereinafter, near-infrared absorbing compositions (D-47) to (D-83) were prepared in the same manner as near-infrared absorbing composition (D-46), except that the near-infrared absorbing dye, resin-type dispersant solution, binder resin solution, and PGMAc were changed to the compositions and amounts shown in Table 2. 4) is another near-infrared absorbing dye shown below.

[0323] [ka] JPEG0007810015000043.jpg196170

[0324] The compositions of the near-infrared absorbing compositions (D-1 to 84) are shown in Table 2. The water content of each of (D-7 to 84) was 0.1 to 2.0 mass% relative to the total amount of the near-infrared absorbing composition, and the content of the specific metal atom was 1 to 1000 mass ppm relative to the total amount of the near-infrared absorbing composition.

[0325] [Table 2]

[0326] <Evaluation of near-infrared absorbing composition> The near-infrared absorbing compositions (D-1 to 84) obtained in the examples and comparative examples were tested for dispersion stability, spectral characteristics, and resistance (light resistance, heat resistance) by the following methods. The results are shown in Table 3.

[0327] (Evaluation of dispersion stability) The viscosity of the obtained near-infrared absorbing composition was measured and defined as the initial viscosity. Further, an accelerated test was carried out at 40°C for 7 days to measure the accelerated viscosity over time. The rate of change due to acceleration was calculated as "accelerated viscosity over time / initial viscosity", and the dispersion stability was evaluated according to the following criteria. ◎: Less than 1.05 ○: 1.05 or more, less than 1.10 △: 1.10 or more, less than 1.3 ×: 1.3 or more

[0328] (Evaluation of spectral characteristics) The obtained near-infrared absorbing composition (D) was spin-coated onto a 1.1 mm thick glass substrate using a spin coater so that the transmittance at 800 nm was 1%, and the substrate was prepared by drying at 60° C. for 5 minutes and then heating at 230° C. for 20 minutes. The absorption spectrum of the obtained substrate was measured in the wavelength range of 400 to 1200 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation). The average transmittance (T) for each range was calculated from the measured absorption spectrum and evaluated according to the following criteria. The evaluation results are shown in Table 3.

[0329] Spectral characteristics 1:480nm~650nm ○: 40% ≦ (T) △: 25% ≦ (T) < 40% ×: (T) < 25% Spectral characteristics 2:700nm~800nm ○: (T) ≦ 5% △: 5% < (T) ≦ 10% ×: 10% < (T) Spectral characteristics 3:900nm~1200nm 〇: 80% ≦ (T) △: 60% ≦ (T) < 80% ×: (T) < 60%

[0330] (Lightfastness test) A test substrate was prepared using the same procedure as in the spectral characteristic evaluation, and placed in a light resistance tester (TOYOSEIKI "SUNTEST CPS+") and left for 24 hours. The absorbance at the largest absorption wavelength was measured, and the remaining ratio to that before light irradiation was calculated, and the light resistance was evaluated according to the following criteria. The remaining ratio was calculated using the following formula. Residual rate = (absorbance after irradiation) ÷ (absorbance before irradiation) × 100 ◎: Residual rate is 95% or more ○: Residual rate is 90% or more, but less than 95% ×: Residual rate is less than 90%

[0331] (Heat resistance test) Test substrates were prepared using the same procedure as in the spectral characteristic evaluation, and were additionally heated at 210°C for 20 minutes as a heat resistance test. The absorbance at the spectral maximum absorption wavelength of the near-infrared absorbing film was measured, and the remaining ratio to that before the heat resistance test was calculated, and the heat resistance was evaluated according to the following criteria. The remaining ratio was calculated using the following formula. Residual rate = (absorbance after heat resistance test) ÷ (absorbance before heat resistance test) × 100 ◎: Residual rate is 95% or more ○: Residual rate is 90% or more, but less than 95% ×: Residual rate is less than 90%

[0332] [Table 3]

[0333] The results in Table 3 show that the near-infrared absorbing composition containing the compound of the present invention has a high ability to cut near-infrared rays from 700 nm to 800 nm (spectral characteristic 2), transmits visible light from 480 nm to 650 nm and near-infrared rays from 900 nm onward (spectral characteristics 1 and 3), has good dispersion stability, and is excellent in light resistance and heat resistance.

[0334] <Production of Photosensitive Near-Infrared Absorbing Composition> [Example 103] (Photosensitive near-infrared absorbing composition (R-1)) The following mixture was mixed and stirred until homogeneous, and then filtered through a 1.0 μm filter. Thus, a photosensitive near-infrared absorbing composition (R-1) was obtained. Near infrared absorbing composition (D-1): 50.0 parts Binder resin 2 solution: 7.5 parts Photopolymerization initiator (Toagosei Co., Ltd. "Aronix M-402"): 2.0 parts Photopolymerization initiator (BASF Japan "OXE-02"): 1.5 parts PGMAc: 39.0 copies

[0335] [Examples 104 to 115 and Comparative Example 3] (Photosensitive near-infrared absorbing compositions (R-2) to (R-14)) Hereinafter, photosensitive near-infrared absorbing compositions (R-2) to (R-14) were obtained in the same manner as for the photosensitive near-infrared absorbing composition (R-1), except that the near-infrared absorbing composition was changed to the type of near-infrared absorbing composition shown in Table 4.

[0336] <Evaluation of Photosensitive Near-Infrared Absorbing Composition> The photosensitive near-infrared absorbing compositions (R-1) to (R-14) obtained in the examples and comparative examples were tested for spectral characteristics and resistance (heat resistance, light resistance) by the following methods. The results are shown in Table 4.

[0337] (Evaluation of dispersion stability) The viscosity of the photosensitive near-infrared absorbing composition thus obtained was measured and recorded as the initial viscosity. Further, an accelerated viscosity test was carried out at 40° C. for 7 days, and the accelerated viscosity over time was measured. The rate of change due to acceleration was calculated as accelerated viscosity / initial viscosity, and evaluated according to the following criteria: ⊚: Less than 1.05 ○: 1.05 or more, less than 1.10 △: 1.10 or more, less than 1.3 ×: 1.3 or more

[0338] (spectral characteristics evaluation) The obtained photosensitive near-infrared absorbing composition (R) was spin-coated onto a 1.1 mm thick glass substrate using a spin coater so that the transmittance at 800 nm was 1%, and the substrate was dried at 60°C for 5 minutes. After that, the substrate was irradiated with 100 mJ / cm using an ultra-high pressure mercury lamp. 2 The substrate was then irradiated with ultraviolet light, spray-developed with an alkaline developer consisting of a 0.2% by mass aqueous solution of sodium carbonate, and then heated for 20 minutes at 230°C to produce a substrate. The absorption spectrum of the obtained substrate was measured in the wavelength range of 400 to 1200 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation). The average transmittance (T) of each range was calculated from the measured absorption spectrum and evaluated according to the same criteria as in the evaluation of the spectral characteristics of the near-infrared absorbing composition (D). The evaluation results are shown in Table 4.

[0339] (Lightfastness test) A test substrate was prepared using the same procedure as in the spectral characteristic evaluation, and the test was performed using a light resistance tester (TOYOSEIKI Co., Ltd.). The film was placed in a container (SUNTEST CPS+ manufactured by Suntest) and left for 24 hours. The absorbance at the largest absorption wavelength was measured, and the remaining ratio to that before light irradiation was calculated, and the light resistance was evaluated according to the following criteria. The remaining ratio was calculated using the following formula. Residual rate = (absorbance after irradiation) ÷ (absorbance before irradiation) × 100 ◎: Residual rate is 95% or more ○: Residual rate is 90% or more, but less than 95% ×: Residual rate is less than 90%

[0340] (Heat resistance test) Test substrates were prepared using the same procedure as in the spectral characteristic evaluation, and were additionally heated at 210°C for 20 minutes as a heat resistance test. The absorbance at the spectral maximum absorption wavelength of the near-infrared absorbing film was measured, and the remaining ratio to that before the heat resistance test was calculated, and the heat resistance was evaluated according to the following criteria. The remaining ratio was calculated using the following formula. Residual rate = (absorbance after heat resistance test) ÷ (absorbance before heat resistance test) × 100 ◎: Residual rate is 95% or more ○: Residual rate is 90% or more, but less than 95% ×: Residual rate is less than 90%

[0341] [Table 4]

[0342] The results in Table 4 show that the photosensitive near-infrared absorbing composition (R) has similar results to the near-infrared absorbing composition (D), having a high ability to cut near-infrared rays from 700 nm to 800 nm (spectral characteristic 2), transmitting visible light from 480 nm to 650 nm and near-infrared light of 900 nm and beyond (spectral characteristics 1 and 3), and also having good dispersion stability and excellent light resistance and heat resistance.

[0343] <Production of near-infrared cut filters> [Examples 116 to 119] (Near-infrared absorption cut filters (F-1) to (F-4)) The photosensitive near-infrared absorbing composition (R-1) of the present invention was applied onto a glass substrate having a thickness of 1.1 mm using a spin coater, and then prebaked by heating on a hot plate at 100° C. for 1 minute. Next, an ultra-high pressure mercury lamp USH-200DP (manufactured by Ushio Inc.) was used to measure the To form a μm square near-infrared absorption cut filter, an exposure dose of 1000 mJ / cm was applied through a photomask. 2 Pattern exposure was carried out. The exposed coating was subjected to shower development using a 0.2% by mass aqueous solution of sodium carbonate as a developer at a developer pressure of 0.1 mPa to remove the uncured portions of the coating, forming a 400 μm × 400 μm pattern. This was then post-baked at 100°C for 120 minutes. The film thickness of the near-infrared absorption cut filter (F-1) after heat treatment was 1.0 μm. For the photosensitive near-infrared absorbing compositions (R-2) to (R-4), near-infrared cut filters (F-2) to (F-4) were obtained in the same manner as for the near-infrared absorption cut filter (F-1).

[0344] <Evaluation of near-infrared cut filters> The near-infrared cut filters (F-1) to (F-4) were subjected to tests on spectral characteristics and durability (heat resistance, light resistance) in the same manner as in the evaluation of the photosensitive near-infrared absorbing composition. The results are shown in Table 5.

[0345] [Table 5]

[0346] The results in Table 5 show that Examples 116 to 119 had excellent spectral properties. They had high transmittance in the visible light region of 480 nm to 650 nm (spectral property 1), excellent near-infrared absorption ability from 700 nm to 800 nm (spectral property 2), and transmission of near-infrared light from 900 nm onward (spectral property 3). They also had excellent light resistance and heat resistance. Therefore, they are suitable for near-infrared cut filters.

[0347] <Production of near-infrared absorbing composition (visible light absorbing composition) containing an organic dye having absorption in the range of 400 nm to 700 nm>

[0348] (Blue colored composition) A mixture of the following composition was stirred and mixed uniformly, dispersed in an Eiger mill using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter to prepare a blue colored composition. CI Pigment Blue PB15:6:10.0 parts Resin-type dispersant solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47.5 parts

[0349] (Purple colored composition) A mixture of the following composition was stirred and mixed uniformly, then dispersed in an Eiger mill using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter to prepare a purple colored composition. CI Pigment Violet PV23: 10.0 parts Resin-type dispersant solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47.5 parts

[0350] (yellow colored composition) A mixture of the following composition was stirred and mixed uniformly, dispersed in an Eiger mill using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a 0.5 μm filter to prepare a yellow colored composition. CI Pigment Yellow PY139: 10.0 parts Resin-type dispersant solution: 7.5 parts Binder resin 1 solution: 35.0 parts PGMAc: 47.5 parts

[0351] [Example 120] (Visible Light-Absorbing Composition (P-1)) The following mixture was stirred and mixed to become uniform, and then filtered through a 1.0 μm filter to obtain a visible light absorbing composition (P-1). Near infrared absorbing composition (D-1): 10.0 parts Blue pigment composition: 20.0 parts Purple pigment composition: 10.0 parts Yellow pigment composition: 10.0 parts Binder resin 1 solution: 7.5 parts Photopolymerization initiator (Toagosei Co., Ltd. "Aronix M-402"): 2.0 parts Photopolymerization initiator (BASF Japan "OXE-02"): 1.5 parts PGMAc

[0352] [Examples 121 to 124] (Visible light region absorbing composition (P-2)~(P-5)) Thereafter, visible light absorbing compositions (P-2) to (P-5) were obtained in the same manner as the visible light absorbing composition (P-1), except that the near-infrared absorbing composition was changed to the type of near-infrared absorbing composition shown in Table 6.

[0353] <Evaluation of Visible Light Absorbing Composition> The obtained visible light absorbing composition was spin-coated onto a 1.1 mm thick glass substrate using a spin coater to a film thickness of 2.0 μm, dried at 60°C for 5 minutes, and then heated at 230°C for 5 minutes to prepare a substrate. The function of the filter is, for example, whether or not it can transmit near-infrared light and whether or not it can cut off light in other wavelength ranges. The transmittance in the wavelength range of 900 to 1200 nm and the absorbance in the wavelength range of 400 to 800 nm were evaluated below.

[0354] (Absorbs from 400 to 800 nm) The transmission spectrum of the obtained substrate was measured in the wavelength range of 400 to 800 nm using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation). ○: Transmittance is less than 2% in the entire range from 400 to 800 nm △: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in the entire range from 400 to 800 nm

[0355] (900~1200nm transmission) The transmittance of the obtained substrate in the range of 900 nm to 1200 nm was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation). ○: Transmittance is 80% or more in the entire range from 900 to 1200 nm △: 40% or more and less than 80% in some regions of 900 to 1200 nm ×: Less than 40% in some regions of 900 to 1200 nm

[0356] (Lightfastness test) The obtained substrate was subjected to a light resistance test using a light resistance tester (TOYOSEIKI "SUNTEST CPS+ The test was carried out using a broadband light source with an irradiance of 47 mW / cm2 and a wavelength range of 300 to 800 nm. The transmittance spectrum was then measured in the wavelength range of 400 to 800 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation). ○: Transmittance is less than 2% in the entire range from 400 to 800 nm △: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in the entire range from 400 to 800 nm

[0357] (Heat resistance test) The obtained substrate was subjected to an additional heat resistance test by heating for 20 minutes at 210° C. Thereafter, the transmission spectrum in the wavelength range of 400 to 800 nm was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation). ○: Transmittance is less than 2% in the entire range from 400 to 800 nm △: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in the entire range from 400 to 800 nm

[0358] [Table 6]

[0359] The results in Table 6 show that Examples 120 to 124 contain both a near-infrared absorbing dye and a dye that absorbs visible light in the 400 to 700 nm range, thereby absorbing light in the entire 400 to 800 nm range and transmitting near-infrared light in the 900 to 1200 nm range. Furthermore, they have excellent light resistance and heat resistance.

[0360] <Production of near-infrared absorbing composition for molding> (Thermoplastic resin (E)) (E-1) Polyester MA-2101M (polyester resin, manufactured by Unitika Ltd., crystalline resin, melting point 264°C) (E-2) Amilan CM3001-N (polyamide resin, manufactured by Toray Industries, crystalline resin, melting point 265°C) (E-3) Iupilon S-3000 (polycarbonate resin, manufactured by Mitsubishi Engineering Plastics Corporation, amorphous resin, glass transition temperature 145°C) (E-4) Topas (cycloolefin resin, manufactured by Polyplastics Co., Ltd., amorphous resin, glass transition temperature 78°C) (E-5) APEL (cycloolefin resin, manufactured by Mitsui Chemicals, amorphous resin, glass transition temperature 135°C) (E-6) ULTEM (Polyetherimide resin, manufactured by Saudi Basic Industries Corporation, amorphous resin, glass transition temperature 217℃)

[0361] [Example 125] (Masterbatch manufacturing) One part of compound (c) and 99 parts of thermoplastic resin (E-1) were fed into a twin-screw extruder (manufactured by The Japan Steel Works, Ltd.) having a screw diameter of 30 mm through the same feed port, melted and kneaded at 300°C, and then cut into pellets using a pelletizer to produce a masterbatch (M-1).

[0362] (film molding) 95 parts of the thermoplastic resin (E-1) diluted with 5 parts of the obtained masterbatch (M-1) was mixed, and the mixture was melt-mixed at a temperature of 300°C using a T-die molding machine (manufactured by Toyo Seiki Seisakusho) to form a film (Q-1) having a thickness of 250 μm.

[0363] [Examples 126 to 155, Comparative Example 4] In the same manner as in Example 125, the materials shown in Table 7 were used to form films (Q-2) to (Q-32) each having a thickness of 250 μm.

[0364] [Table 7]

[0365] <Evaluation of near-infrared absorbing molding composition>

[0366] (spectral characteristics evaluation) The absorption spectrum of the obtained film was measured in the wavelength range of 400 to 1200 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation). The average transmittance (T) in each range was calculated from the measured absorption spectrum and evaluated according to the following criteria. The evaluation results are shown in Table 8.

[0367] Spectral characteristics 1:480nm~650nm ○: 40% ≦ (T) △: 25% ≦ (T) < 40% ×: (T) < 25% Spectral characteristics 2:700nm~800nm ○: (T) ≦ 5% △: 5% < (T) ≦ 10% ×: 10% < (T) Spectral characteristics 3:900nm~1200nm 〇: 80% ≦ (T) △: 60% ≦ (T) < 80% ×: (T) < 60%

[0368] (transparency) The transparency of the obtained film was evaluated visually. 〇: No turbidity observed at all. △: Slight turbidity observed. ×: Clear turbidity is observed.

[0369] (Lightfastness) A test film was prepared using the same procedure as in the near-infrared absorption evaluation, and placed in a light resistance tester (TOYOSEIKI "SUNTEST CPS+") at an irradiance of 47 mW / cm. 2 , 30 The film was irradiated with broadband light of 0 to 800 nm and left for 24 hours. The test film was then removed and the absorbance at the maximum absorption wavelength of the test film was measured. The residual ratio to the absorbance before light irradiation was calculated, and the light resistance was evaluated according to the following criteria. The residual ratio was calculated using the following formula. Residual rate = (absorbance after irradiation) ÷ (absorbance before irradiation) × 100 ○: Residual rate is 90% or more △: Residual rate is 85% or more but less than 90% ×: Residual rate is less than 85%

[0370] [Table 8]

[0371] From the results in Table 8, Examples 125 to 155 have high transmittance in the visible light region of 480 nm to 650 nm (spectral characteristic 1), excellent near-infrared absorption ability from 700 nm to 800 nm (spectral characteristic 2), transmittance of near-infrared light from 900 nm onwards (spectral characteristic 3), and further have excellent transparency and light resistance.

[0372] <Production of visible light absorbing composition for molding> [Example 156] (Masterbatch manufacturing) One part of compound (c), one part of Pigment Blue 15:3, one part of Pigment Yellow 147, one part of Solvent Red 52, and 96 parts of thermoplastic resin (E-1) were fed into a twin-screw extruder (manufactured by The Japan Steel Works, Ltd.) having a screw diameter of 30 mm through the same supply port, melt-kneaded at 300°C, and then cut into pellets using a pelletizer to prepare a masterbatch (MP-1).

[0373] (film molding) 95 parts of the dilution resin thermoplastic resin (E-1) was mixed with 5 parts of the obtained masterbatch (MP-1), and the mixture was melt-mixed at a temperature of 300°C using a T-die molding machine (manufactured by Toyo Seiki Seisakusho) to form a film (QP-1) with a thickness of 250 μm.

[0374] [Examples 157 to 173] In the same manner as in Example 156, the materials shown in Table 9 were used to form films (QP-2) to (QP-18) each having a thickness of 250 μm.

[0375] [Table 9]

[0376] The obtained film was evaluated for suitability as a near-infrared filter. The filter function is, for example, whether it can transmit near-infrared rays and whether it can block light in other wavelength ranges. The transmittance in the wavelength range of 900 to 1200 nm and the absorbance in the wavelength range of 400 to 800 nm were evaluated below.

[0377] (Absorbs from 400 to 800 nm) The transmission spectrum of the obtained film was measured in the wavelength range of 400 to 800 nm using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation). ○: Transmittance is less than 2% in the entire range from 400 to 800 nm △: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in the entire range from 400 to 800 nm

[0378] (900~1200nm transmission) The transmittance of the obtained film in the range of 900 to 1200 nm was measured using a spectrophotometer (U-4100 manufactured by Hitachi High-Technologies Corporation). ○: Transmittance is 80% or more in the entire range from 900 to 1200 nm △: 40% or more and less than 80% in some regions of 900 to 1200 nm ×: Less than 40% in some regions of 900 to 1200 nm

[0379] (transparency) The transparency of the obtained film was evaluated visually. 〇: No turbidity observed at all. △: Slight turbidity observed. ×: Clear turbidity is observed.

[0380] (Lightfastness) The obtained film was subjected to a lightfastness test using a lightfastness tester (TOYOSEIKI "SUNTEST CP The test was carried out using a broadband light source with an irradiance of 47 mW / cm² and a wavelength range of 300 to 800 nm. The transmittance spectrum was then measured in the wavelength range of 400 to 800 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation). ○: Transmittance is less than 2% in the entire range from 400 to 800 nm △: Transmittance is 2% or more in some regions of 400 to 800 nm ×: Transmittance is 2% or more in the entire range from 400 to 800 nm

[0381] [Table 10]

[0382] From the results in Table 10, it can be seen that Examples 156 to 173 contain both a near-infrared absorbing dye and a dye that absorbs visible light in the 400 to 700 nm range, thereby absorbing light in the entire 400 to 800 nm range and transmitting near-infrared light in the 900 to 1200 nm range. Furthermore, they are excellent in transparency and light resistance.

Claims

1. A compound represented by the following general formula (1) or (2): 【Chemistry 1】 [In the formula, X １ ~X ４０ each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted arylalkyl group, an optionally substituted cycloalkyl group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an amino group, an optionally substituted alkylamino group, an optionally substituted arylamino group, a cyano group, a halogen atom, a nitro group, a hydroxyl group, -SO 3 H; —COOH; and monovalent to trivalent of these acidic groups Metal salt: represents an alkylammonium salt. １ ~X ４０ Two adjacent groups among the groups represented by the formula (I) may be linked to form a 5- or 6-membered ring together with the carbon atoms to which they are bonded. M represents a metal atom.

2. 2. The compound according to claim 1, wherein M is a divalent metal atom.

3. A near-infrared absorbing dye comprising the compound according to claim 1 or 2.

4. A near-infrared absorbing composition comprising the near-infrared absorbing dye according to claim 3 and a binder resin.

5. 5. The near-infrared absorbing composition according to claim 4, wherein the water content in the near-infrared absorbing composition is 0.1 to 2.0% by mass based on the total mass of the near-infrared absorbing composition.

6. The near-infrared absorbing composition contains an element selected from Li, Na, K, Cs, Ca, Fe, and Zr.

6. The near-infrared absorbing composition according to claim 4, further comprising a metal component containing a metal atom, wherein the total amount of the metal atoms in the metal component is 1 to 1000 ppm by mass with respect to the entire near-infrared absorbing composition.

7. 7. The near-infrared absorbing composition according to claim 4, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

8. 8. The near-infrared absorbing composition according to claim 4, further comprising an organic dye having absorption in the range of 400 nm to 700 nm.

9. An optical filter comprising a coating formed from the near-infrared absorbing composition according to any one of claims 4 to 8.

Images