Isoindolin compounds and their applications

Abstract

To provide: novel isoindoline compounds that serve as near-infrared absorbing dyes and that are excellent in heat resistance and light resistance; and, by employing the compounds, compositions, optical filters, infrared cameras, solid-state imaging elements, infrared sensors, laminates, compositions for plastics, plastic molded articles, organic semiconductor inks, films, organic semiconductor devices, and organic photodetectors.SOLUTION: The problem is solved by an isoindoline compound (A) represented by a general formula (1) in the figure.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to an isoindoline compound and its use. [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 ray blocking films, dyes for optical recording, optical character reading and recording, protection against copying of confidential documents, electrophotographic photoreceptors, laser fusion, organic photodetectors, and the like.

[0003] Among these, infrared cut filters for camera sensors are required to have extremely high heat resistance and light resistance, as they are used in vehicles in harsh environments and in devices that require processing at high temperatures.

[0004] Near-infrared absorbing dyes used in near-infrared absorbing materials generally have a maximum absorption wavelength on the longer wavelength side than 700 nm. Representative near-infrared absorbing dyes include cyanine dyes (e.g., Patent Document 1), diimonium dyes (e.g., Patent Document 2), and squarylium dyes (e.g., Patent Document 3). However, these dyes have low heat resistance and light resistance, and poor durability in various environments, so their applications are limited. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Patent Publication No. 2015-172102 [Patent Document 2] Patent Publication No. 2007-92060 [Patent Document 3] Patent Publication No. 2021-177243 Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention aims to provide a novel isoindoline compound, which is a near-infrared absorbing dye having excellent heat resistance and light resistance, a composition using the compound, an optical filter, an infrared camera, a solid-state imaging element, an infrared sensor, a laminate, a composition for plastics, a plastic molded product, an organic semiconductor ink, a film, an organic semiconductor device, and an organic photodetector. [Means for solving the problem]

[0007] As a result of extensive research aimed at solving the above-mentioned problems, the present inventors have found that an isoindoline compound (A) represented by general formula (1) has near-infrared absorption properties and is excellent in heat resistance and light resistance, thereby completing the present invention.

[0008] That is, the present invention relates to an isoindoline compound (A) represented by the following general formula (1). General formula (1) [ka] [In formula (1), X 1 and X 2 represents an oxygen atom or a sulfur atom, X 3 and X 4 is an oxygen atom, a sulfur atom, or NR 101 Represents R 101 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent; Y 1 ~Y 8each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an amide group, a sulfonamide group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group, * 1 and* 2 are independently an oxygen atom, C(CN) 2 , represents a bond to general formula (2), general formula (3), or general formula (4). General formula (2) [ka] [In formula (2), X represents -O- or -NH-; R 1 represents an alkyl group or an aryl group. * represents a bonding site with general formula (1). General formula (3) [ka] [In formula (3), R 2 ~R 6 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, or an aryl group. * represents a bonding site with general formula (1). General formula (4) [ka] [In formula (4), Z represents a ring structure, When Z has multiple substituents, the multiple substituents may be the same or different. * represents a bonding site with general formula (1).

[0009] The present invention also relates to a composition comprising the isoindoline compound (A) and a resin.

[0010] The present invention also relates to the composition, further comprising an organic solvent.

[0011] The present invention also relates to the above composition, which further comprises a photopolymerizable monomer and / or a photopolymerization initiator.

[0012] The present invention also relates to an optical filter having a coating formed from the above composition.

[0013] The present invention also relates to an infrared camera having the optical filter.

[0014] The present invention also relates to a solid-state imaging device having the optical filter.

[0015] The present invention also relates to an infrared sensor having the optical filter.

[0016] The present invention also relates to a laminate comprising the above-mentioned composition.

[0017] The present invention also relates to a composition for plastics, comprising the composition.

[0018] The present invention also relates to a plastic molded article comprising the composition for plastics.

[0019] The present invention also relates to an organic semiconductor ink containing the isoindoline compound (A), a p-type organic semiconductor compound, an n-type organic semiconductor compound, and an organic solvent.

[0020] The present invention also relates to a coating formed from the organic semiconductor ink.

[0021] The present invention also relates to an organic semiconductor device having the coating.

[0022] The present invention also relates to an organic semiconductor device, wherein a photoelectric conversion layer is the above-mentioned coating film.

[0023] The present invention also relates to an organic photodetector using the organic semiconductor device. Effect of the Invention

[0024] The present invention can provide a novel isoindoline compound which is a near-infrared absorbing dye having excellent heat resistance and light resistance, a composition using the compound, an optical filter, an infrared camera, a solid-state imaging device, an infrared sensor, a laminate, a composition for plastics, a plastic molded product, an organic semiconductor ink, a film, an organic semiconductor device, and an organic photodetector. [Brief description of the drawings]

[0025] [Figure 1] FIG. 1 is a schematic cross-sectional view of a photoelectric conversion device provided with a coating of the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] The terms used in this specification are defined below. When "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" is used, it means "acryloyl and / or methacryl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively, unless otherwise specified. In this specification, "CI" means Color Index (CI). Dyes include pigments and dyes.

[0027] <<<Isoindoline compound (A) represented by general formula (1)>>> The isoindoline compound (A) of the present invention represented by general formula (1) will be described below. Hereinafter, the isoindoline compound (A) or compound (A) have the same meaning. General formula (1) [ka]

[0028] In formula (1), X 1 and X 2 represents an oxygen atom or a sulfur atom, X 3 and X 4 is an oxygen atom, a sulfur atom, or NR 101 Represents R 101 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent; Y 1 ~Y 8 each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an amide group, a sulfonamide group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group, * 1 and* 2 are independently an oxygen atom, C(CN) 2 , represents a bond to general formula (2), general formula (3), or general formula (4).

[0029] Y 2 and Y 3 , or Y 6 and Y 7 may be bonded to each other to form an aromatic ring which may have a substituent.

[0030] Examples of halogen atoms include fluorine, chlorine, bromine, and iodine atoms.

[0031] Examples of the "alkyl group" of the alkyl group which may have a substituent include linear or branched alkyl groups such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, neopentyl, n-hexyl, n-octyl, stearyl, and 2-ethylhexyl. Examples of the "alkyl group having a substituent" include trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-dibromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, and 2,4-dichlorobenzyl.

[0032] The amide group is a group in which an amide group is linked to the above-mentioned alkyl group.

[0033] The sulfonamide group is a group in which a sulfonamide group is linked to the above-mentioned alkyl group.

[0034] Examples of the "aryl group" of the aryl group which may have a substituent include a phenyl group, a naphthyl group, and anthryl group. 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, 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.

[0035] Examples of the "cycloalkyl group" of the cycloalkyl group which may have a substituent include a cyclopentyl group, a cyclohexyl group, an adamantyl group, and the like. Examples of the "substituted cycloalkyl group" include a 2,5-dimethylcyclopentyl group, a 4-tert-butylcyclohexyl group, and the like.

[0036] Examples of the "heterocyclic group" of the heterocyclic group which may have a substituent include a pyridyl group, a pyrazyl group, a piperidino group, a pyranyl group, a morpholino group, an acridinyl group, etc. Examples of the "heterocyclic group having a substituent" include a 3-methylpyridyl group, an N-methylpiperidyl group, an N-methylpyrrolyl group, etc.

[0037] Examples of the "alkoxyl group" in the alkoxyl group which may have a substituent include straight-chain 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.

[0038] 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. Examples of the "substituted aryloxy group" include a p-methylphenoxy group, a p-nitrophenoxy group, a p-methoxyphenoxy group, a 2,4-dichlorophenoxy group, a pentafluorophenoxy group, and a 2-methyl-4-chlorophenoxy group.

[0039] 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.

[0040] 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.

[0041] General formula (2) [ka]

[0042] In formula (2), X represents -O- or -NH-; R 1 represents the above-mentioned alkyl group or aryl group. * represents a bonding site with general formula (1).

[0043] From the viewpoints of heat resistance, light resistance, and dispersion stability, X is preferably -NH-, and the alkyl group is preferably an alkyl group having 1 to 4 carbon atoms, more preferably an alkyl group having 1 or 2 carbon atoms.

[0044] General formula (3) [ka]

[0045] In formula (3), R 2 ~R 6 R each independently represents a hydrogen atom, a halogen atom, an alkyl group, an alkoxyl group, or an aryl group. 2 ~R 6 In the formula (I), the halogen atom, the alkyl group, the alkoxy group, or the aryl group is Y1 ~Y 8 The symbol * represents the bonding site with general formula (1).

[0046] General formula (4) [ka]

[0047] In formula (4), Z represents a ring structure, and when ring Z has multiple substituents, the multiple substituents may be the same or different. * represents a bonding site with general formula (1).

[0048] Ring Z is preferably one used as an acidic nucleus in a merocyanine dye or a ring represented by any of the general formulae (5) to (10).

[0049] Examples of merocyanine dyes that can be used as acidic nuclei include the following. (a) 1,3-dicarbonyl nucleus: for example, 1,3-indandione, 1,3-dioxane-4,6-dione, etc. (b) Pyrazolinone nucleus: for example, 1-phenyl-2-pyrazolin-5-one, 3-methyl-1-phenyl-2-pyrazolin-5-one, 1-(2-benzothiazoyl)-3-methyl-2-pyrazolin-5-one, etc. (c) Isoxazolinone nucleus: For example, 3-phenyl-2-isoxazolin-5-one, 3-methyl-2-isoxazolin-5-one, etc. (d) Oxindole nucleus: For example, oxindole, 1-alkyl-2,3-dihydro-2-oxindole, 1-ethylindolin-2-one, etc. (e) 2,4,6-triketohexahydropyrimidine nucleus: For example, barbituric acid or 2-thiobarbituric acid and derivatives thereof. Examples of derivatives include 1-alkyl compounds such as 1-methyl and 1-ethyl, acyl compounds such as acetyl, 1,3-dialkyl compounds such as 1,3-dimethyl, 1,3-diethyl and 1,3-dibutyl, 1,3-diaryl compounds such as 1,3-diphenyl, 1,3-di(p-chlorophenyl) and 1,3-di(p-ethoxycarbonylphenyl), 1-alkyl-1-aryl compounds such as 1-ethyl-3-phenyl, and 1,3-diheterocyclic compounds substituted at the 1,3-positions such as 1,3-di(2-pyridyl). (f) 2-thio-2,4-thiazolidinedione nucleus: For example, rhodanine and its derivatives, etc. Examples of the derivatives include 3-alkylrhodanines such as 3-methylrhodanine, 3-ethylrhodanine, and 3-arylrhodanine, 3-arylrhodanines such as 3-phenylrhodanine, and 3-position-heterocyclic substituted rhodanines such as 3-(2-pyridyl)rhodanine. (g) 2-thio-2,4-oxazolidinedione (2-thio-2,4-(3H,5H)-oxazoledione nucleus): for example, 3-ethyl-2-thio-2,4-oxazolidinedione, etc. (h) Thianaphthenone nucleus: For example, 3(2H)-thianaphthenone-1,1-dioxide, etc. (i) 2-thio-2,5-thiozolidinedione nucleus: for example, 3-ethyl-2-thio-2,5-thiazolidinedione, etc. (j) 2,4-Thiozolidinedione nucleus: For example, 2,4-thiazolidinedione, 3-ethyl-2,4-thiazolidinedione, 3-phenyl-2,4-thiazolidinedione, etc. (k) Thiazolin-4-one nucleus: for example, 4-thiazolinone, 2-ethyl-4-thiazolinone, etc. (l) 4-thiazolidinone nucleus: for example, 2-ethylmercapto-5-thiazolin-4-one, 2-alkylphenylamino-5-thiazolin-4-one, etc. (m) 2,4-imidazolidinedione (hydantoin) nucleus: For example, 2,4-imidazolidinedione, 3-ethyl-2,4-imidazolidinedione, and the like. (n) 2-thio-2,4-imidazolidinedione (2-thiohydantoin) nucleus: for example, 2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio-2,4-imidazolidinedione, etc. (o) Imidazolin-5-one nucleus: for example, 2-propylmercapto-2-imidazolin-5-one, and the like. (p) 3,5-pyrazolidinedione nucleus: For example, 1,2-diphenyl-3,5-pyrazolidinedione, 1,2-dimethyl-3,5-pyrazolidinedione, etc. (q) Benzothiophen-3-one nucleus: for example, benzothiophen-3-one, oxobenzothiophen-3-one, dioxobenzothiophen-3-one, etc. (r) Indanone nucleus: for example, 1-indanone, 3-phenyl-1-indanone, 3-methyl-1-indanone, 3,3-diphenyl-1-indanone, 3,3-dimethyl-1-indanone, 3-(dicyanomethylidene)indan-1-one, (5,6-difluoro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile, (5,6-dichloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile, and the like.

[0050] [ka]

[0051] In formulas (5) to (9), R 15 ~R 27represents a hydrogen atom or a monovalent substituent, and the monovalent substituent is an alkyl group (an alkyl group having 1 to 12 carbon atoms, such as a methyl group, an ethyl group, a butyl group, an isopropyl group, a t-butyl group, a hydroxyethyl group, a methoxyethyl group, a cyanoethyl group, a trifluoromethyl group, a 3-sulfopropyl group, or a 4-sulfobutyl group), a cycloalkyl group (for example, a cyclohexyl group or a cyclopentyl group), an aralkyl group (for example, a benzyl group or a 2-phenethyl group), an aryl group (for example, a phenyl group, a p-tolyl group, a p-methacrylate group, or a methyl group), Examples of the aromatic hydrocarbon group include aryloxy groups (e.g., phenyloxy groups, o-phenyloxy groups, m-(3-sulfopropylamino)phenyl groups), heterocyclic groups (e.g., 2-pyridyl groups, 2-thienyl groups, 2-furyl groups), alkoxy groups (alkoxy groups having 1 to 12 carbon atoms, e.g., methoxy groups, ethoxy groups, isopropoxy groups, methoxyethoxy groups, hydroxyethoxy groups, 3-carboxypropoxy groups), aryloxy groups (e.g., phenoxy groups, p-methoxyphenyl groups, o-methoxyphenoxy groups, etc.), acylamino groups (e.g., acetylamino groups, propoxy groups, etc.), Examples of the aryl group include a phenyl group, ... Examples of the alkyl group include aryl groups (e.g., phenyl, p-tolylthio groups), alkoxycarbonyl groups (e.g., methoxycarbonyl groups, ethoxycarbonyl groups), carbamoyl groups (e.g., methylcarbamoyl groups, dimethylcarbamoyl groups), sulfamoyl groups (e.g., dimethylsulfamoyl groups, di-2-hydroxyethyl)sulfamoyl groups), sulfonyl groups (e.g., methanesulfonyl groups, benzenesulfonyl groups), acyl groups (e.g., acetyl groups, benzoyl groups), and amino groups (e.g., methylamino groups, diethylamino groups). In formula (10), R 28 represents an oxygen atom or -NH, and R 11 ~R 14 , and R29 ~R 32 each independently represents a hydrogen atom, a halogen atom, a hydroxyl group, a carboxyl group, a nitro group, an alkyl group, an alkoxy group, an aryl group, an aryloxy group, a thioalkyl group, a thioaryl group, an amide group, or a sulfonamide group. 5 ~X 8 represents an oxygen atom or a sulfur atom.

[0052] Ring Z is preferably a ring represented by formula (10), or a 1,3-dicarbonyl nucleus, an oxindole nucleus, a 2,4,6-triketohexahydropyrimidine nucleus, a thianaphthenone nucleus, or an indanone nucleus that is used as an acidic nucleus in a merocyanine dye. When the bond is one of these, an isoindoline compound (A) having excellent heat resistance and light resistance can be obtained by intramolecular hydrogen bonding.

[0053] The substituents on ring Z include Y 1 ~Y 8 Examples of the groups include those having the same meanings as those explained under .

[0054] In general formula (1), * 1 , and * 2 The atoms or compounds represented by may be the same or different.

[0055] The synthesis method of the compound represented by the general formula (1) is described below. The compound represented by the general formula (1) can be obtained by reacting 3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione (hereinafter, BzDF) with a compound represented by the following general formula (11) in a solvent. The compound represented by the general formula (11) can be obtained according to the synthesis method described in JP-A-2020-180176.

[0056] General formula (11) [ka]

[0057] In formula (11), Y-9 ~Y 12 each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an amide group, a sulfonamide group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group; Y 10 and Y 11 may be bonded to each other to form an aromatic ring which may have a substituent, and * represents a bond to any of the general formulae (2) to (4).

[0058] The reaction temperature is not particularly limited, but is preferably in the range of 20 to 150°C.

[0059] The reaction solvent is not particularly limited, but glacial acetic acid or N-methyl-2-pyrrolidone is preferable, and two or more reaction solvents may be mixed.

[0060] The reaction time is not particularly limited, but the progress of the reaction may be confirmed by LC / MS spectroscopy or a spectrophotometer to confirm the disappearance of the raw materials.

[0061] The isoindoline compound (A) represented by the general formula (1) has a maximum absorption wavelength in the wavelength range of 700 nm or more and 1000 nm or less, and therefore has near-infrared absorptivity and functions excellently as a near-infrared absorbing dye.

[0062] In the present invention, examples of the isoindoline compound (A) represented by general formula (1) include the following compounds, but the present invention is not limited thereto.

[0063] [ka]

[0064] [ka]

[0065] [ka]

[0066] <<Composition>> The composition of the present invention contains an isoindoline compound (A) represented by general formula (1) and a resin.

[0067] The content of the isoindoline compound (A) represented by general formula (1) in the composition of the present invention is preferably in the range of 1 to 70% by mass, with the total weight of the composition being 100% by mass. When other dyes are used in combination, the mass ratio of other dyes / isoindoline compound (A) represented by general formula (1) is preferably in the range of 5 / 95 to 50 / 50.

[0068] <Other dyes> The dye in this specification refers to the isoindoline compound (A) represented by general formula (1) and other dyes. The composition of the present invention may contain other dyes other than the isoindoline compound (A) represented by general formula (1). Examples of other dyes include organic dyes having a maximum absorption wavelength in the wavelength range of 400 nm to 700 nm, and near-infrared absorbing dyes having a maximum absorption wavelength in the wavelength range of more than 700 nm to 2000 nm.

[0069] (An organic dye with a maximum absorption wavelength between 400nm and 700nm) Examples of organic dyes having a maximum absorption wavelength in the range of 400 nm or more and 700 nm or less 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, anthranthrone, indanthrone, pyranthrone, or violanthrone, quinacridone pigments, perinone pigments, thioindigo pigments, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, phthalocyanine pigments, threne pigments, and metal complex pigments. In addition, dyes may be used as the organic coloring matter, and examples of such dyes 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 dyes into the resin using the polar groups of anionic dyes or cationic dyes to impart solubility in organic solvents.

[0070] 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, 79, and 80.

[0071] 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.

[0072] 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, 129130, Also included are 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, and 263.

[0073] 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.

[0074] 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 Bat Green 3, 6, and 8.

[0075] 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.

[0076] 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, 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.

[0077] 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.

[0078] 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.

[0079] 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, and the like.

[0080] 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.

[0081] 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, 1 01, 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, 22 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.

[0082] As orange pigments which function similarly to red pigments, for example, orange pigments such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 73, etc. can be used.

[0083] 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, 109, 109, 108, 109, 109, 102, 103, 104, 105, 106, 107, 108, 109, 109, 109, 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, 1 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, 24 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.

[0084] 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, 109, 109, 102, 103, 104, 105, 106, 107, 108, 109, 109, 102, 103, 104, 105, 106, 107, 108, 10 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, Also included are 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.

[0085] Further examples include CI Solvent Red 52, 135, 146, 149, 168, 179, 207, and the like.

[0086] Although the above dyes have good spectral characteristics and excellent color development, they have problems with heat resistance and light resistance, and their characteristics may not be sufficient for use in optical filters. Therefore, in order to overcome these drawbacks, in the case 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 compound having a cationic group or a resin having a cationic group as a counter ion to form a salt, from the viewpoints of heat resistance, light fastness, and solvent resistance. It is also preferable to use the compound by forming a salt with a resin having a cationic group, and more preferably to use the compound by forming a salt with a resin having a cationic group on the side chain and an organic acid. In addition, it is also preferable in terms of durability to use an anionic dye as a sulfonamide compound by sulfonamidation. 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.

[0087] (Near infrared absorbing dye with a maximum absorption wavelength of more than 700 nm and less than 2000 nm) The near infrared absorbing colorant having a maximum absorption wavelength of more than 700 nm and not more than 2000 nm may be either a near infrared absorbing dye or a near infrared absorbing pigment, and may be either an inorganic pigment or an organic pigment. From the viewpoints of heat resistance and light resistance, it is preferable that it is an organic pigment.

[0088] Examples of inorganic pigments as near infrared absorbing pigments include metal oxides and metal borides. Examples of metal oxides include indium tin oxide, antimony tin oxide, zinc oxide, Al-doped zinc oxide, fluorine-doped tin dioxide, niobium-doped titanium dioxide, and tungsten oxide. For details of tungsten oxide, refer to paragraph 0080 of JP2016-006476A, the contents of which are incorporated herein by reference. Examples of metal borides include lanthanum boride. Examples of commercially available lanthanum boride include LaB6-F (manufactured by Japan New Metals Co., Ltd.). In addition, compounds described in International Publication WO2017 / 119394 can also be used as metal borides. Examples of commercially available indium tin oxide include F-ITO (manufactured by DOWA High-Tech Co., Ltd.).

[0089] Examples of near-infrared absorbing pigments as organic pigments include pyrrolopyrrole compounds, polymethine compounds, diimonium compounds, dithiolene compounds, phthalocyanine compounds, porphyrin compounds, azo compounds, triarylmethane compounds, perylene compounds, croconium compounds, etc. Examples of polymethine compounds include cyanine compounds, squarylium compounds, croconium compounds, oxonol compounds, etc.

[0090] Among the coloring matters, pigments can be used after being pulverized. The method of pulverization is not particularly limited, and any of wet grinding, dry grinding, dissolution precipitation, and the like can be used.

[0091] The salt milling treatment, which is one type of wet grinding exemplified in the present invention, is a treatment in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while being heated using, for example, a batch or continuous kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or a planetary mixer, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed during salt milling by utilizing the high hardness of the inorganic salt. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

[0092] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. Among these, sodium chloride (table salt) is preferred from the viewpoint of cost. The amount of the water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, and more preferably 300 to 1000 parts by mass, per 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

[0093] The water-soluble organic solvent moistens the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound that dissolves (is mixed) in water and does not substantially dissolve the water-soluble inorganic salt. The water-soluble organic solvent is preferably a high-boiling solvent having a boiling point of 120°C or more, in that it is less likely to volatilize due to the temperature rise during salt milling. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, relative to 100 parts by mass of the pigment.

[0094] During the salt milling treatment, a resin can be added as necessary. Examples of the resin include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in a water-soluble solvent. The amount of the resin used is preferably 5 to 200 parts by mass relative to 100 parts by mass of the pigment.

[0095] By subjecting the pigment to salt milling treatment, it is possible to more uniformly pulverize the pigment, thereby improving the coloring power, transmittance, and dispersion stability in a well-balanced manner.

[0096] <Derivative (B)> The composition of the present invention may contain a single derivative or two or more derivatives in combination. The derivative is a compound having a structure in which a part of the dye skeleton is substituted with an acidic group, a basic group, or a phthalimidomethyl group. From the viewpoint of dispersibility and dispersion stability, the derivative is preferably a derivative having an acidic group or a basic group. As the acidic group of the dye derivative, sulfonic acid, carboxylic acid, and quaternary ammonium salts thereof are preferred, carboxylic acid groups and sulfonic acid groups are more preferred, and sulfonic acid groups are even more preferred. As the basic group of the derivative, an amino group is preferred, and a tertiary amino group is even more preferred.

[0097] <Resin> The composition of the present invention contains a resin. The resin preferably has a spectral transmittance of 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm in the visible light region when a coating film having a thickness of 2 μm is formed. Examples of the resin include a resin-type dispersant (C) and a binder resin (D).

[0098] (Resin-type dispersant (C)) As the resin in the present invention, a known resin-type dispersant (C) can be used. The resin-type dispersant (C) may be any dispersant that has a dye affinity site that has the property of adsorbing to the added dye and a site that is compatible with the dye carrier, and that functions to adsorb to the dye and stabilize its dispersion in the dye carrier.Specific examples of the dispersant include urethane-based dispersants such as polyurethane, polycarboxylate esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphate salts, hydroxyl group-containing polycarboxylate esters, and modified products thereof, oil-based dispersants such as amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups and their salts, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyester-based compounds, modified polyacrylate-based compounds, ethylene oxide / propylene oxide adducts, and phosphate-based compounds, which may be used alone or in combination of two or more.

[0099] Preferred examples of the resin-type dispersant (C) having an acidic functional group include resin-type dispersants having an aromatic carboxylic acid structure, which can be produced by known methods such as those described in WO2008 / 007776, JP2008-029901A, JP2009-155406A, JP2010-185934A, JP2011-157416A, JP2009-251481A, JP2007-23195A, and JP1996-143651A.

[0100] Preferred examples of the resin-type dispersant (C) having a basic functional group include nitrogen-atom-containing graft copolymers, and nitrogen-atom-containing acrylic block copolymers and urethane-based polymer dispersants having functional groups in the side chains including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc.

[0101] As disclosed in JP 2009-185277 A, a preferred example is the combined use of a resin-type dispersant (C) having an aromatic carboxyl group and a vinyl resin (having the function of a resin-type dispersant (C)) having a tertiary amino group.

[0102] The resin-type dispersant (C) is preferably used in an amount of about 3 to 200% by mass based on the total amount of the dye, and from the viewpoint of film-forming properties, more preferably about 5 to 100% by mass.

[0103] From the viewpoint of storage stability, the resin-type dispersant (C) is preferably a resin-type dispersant (C) having a basic functional group, whereas from the viewpoint of developability, the resin-type dispersant (C) is preferably a resin-type dispersant (C) having an acidic functional group.

[0104] The resin-type dispersant (C) can be used alone or in combination of two or more kinds.

[0105] (Binder resin (D)) The resin in the present invention may contain a binder resin (D). Examples of the binder resin (D) include a thermoplastic resin and a photosensitive resin.

[0106] 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, polyimide resins, polyolefin resins, polyamide resins, polycarbonate resins, cycloolefin resins, polyetherimide resins, and the like. Thermoplastic resins suitable for molding applications are described below.

[0107] Examples of photosensitive resins include resins obtained by reacting a polymer having a reactive substituent such as a hydroxyl group, a carboxyl group, or an amino group with a (meth)acrylic compound having a reactive substituent such as an isocyanate group, an aldehyde group, or an epoxy group, or with cinnamic acid to introduce a photocrosslinkable group such as a (meth)acryloyl group or a styryl group into the polymer. Other examples include resins obtained by half-esterifying a polymer containing an acid anhydride, such as a styrene-maleic anhydride copolymer or an α-olefin-maleic anhydride copolymer, with a (meth)acrylic compound having a hydroxyl group, such as a hydroxyalkyl (meth)acrylate.

[0108] The coating formed from the composition is preferably patterned by photolithography, or melt-kneaded to produce a film or the like. The binder resin (D) in the coating formed by patterning by photolithography is preferably an alkali-soluble resin. The alkali-soluble resin can be used as a photosensitive alkali-soluble resin by providing a polymerizable unsaturated group. The binder resin (D) in the coating formed by melt-kneading to produce a film or the like is preferably a moldable thermoplastic resin (D1).

[0109] Examples of the alkali-soluble resin include resins having an acidic group such as a carboxyl group or a sulfonic group. Examples of the alkali-soluble resin 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 functional group and styrene / styrene sulfonic acid copolymers are preferred in terms of good transparency, and acrylic resins having an acidic functional group are more preferred.

[0110] The photosensitive alkali-soluble resin is preferably a resin synthesized by, for example, the following method (i) or (ii), which further improves the crosslink density of the coating film formed from the composition upon irradiation with light.

[0111] [Method (i)] In the method (i), for example, a polymer of an epoxy group-containing monomer and another monomer is first synthesized, and then a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and a polybasic acid anhydride is reacted with the generated hydroxyl group to obtain an alkali-soluble resin.

[0112] Examples of epoxy group-containing monomers 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.

[0113] Examples of monocarboxyl group-containing monomers 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.

[0114] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0115] The monomers and polybasic acid anhydrides can each be used alone or in combination of two or more kinds.

[0116] As a method similar to method (i), for example, a carboxyl group-containing monomer and other monomers are synthesized to prepare a polymer, and then an epoxy group-containing monomer is added to a part of the carboxyl groups of the polymer to obtain a photosensitive alkali-soluble resin.

[0117] [Method (ii)] In the method (ii), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to prepare a polymer, and then the hydroxyl group of the polymer is reacted with an isocyanate group of an isocyanate group-containing monomer.

[0118] Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, or cyclohexane dimethanol mono(meth)acrylate. In addition, examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above-mentioned hydroxyalkyl (meth)acrylates, and (poly)ester mono(meth)acrylates obtained by addition of (poly)γ-valerolactone, (poly)ε-caprolactone, and / or (poly)12-hydroxystearic acid. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred. In addition, glycerol mono(meth)acrylate is preferred in terms of photosensitivity.

[0119] Examples of monomers having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0120] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably 5,000 to 100,000, more preferably 7,000 to 50,000. When used as an alkali-soluble resin, if the weight average molecular weight is 5,000 to 100,000, the film is less likely to be reduced during development, and non-pixel areas are more likely to be removed during development. The number average molecular weight (Mn) is preferably 2,500 to 40,000. The value of Mw / Mn is preferably 10 or less. Mw and Mn are polystyrene-equivalent molecular weights measured using a gel permeation chromatography (GPC) device HLC-8220GPC (manufactured by Tosoh Corporation) and two TSK-GELSUPERHZM-N columns connected in series, with tetrahydrofuran as the solvent.

[0121] The acid value of the alkali-soluble resin is preferably 20 to 300 mgKOH / g. If the resin has a suitable acid value, the developability is improved.

[0122] The amount of the alkali-soluble resin used is preferably 20 to 500 parts by mass per 100 parts by mass of the dye. When an appropriate amount is used, the formation of a coating film becomes easy.

[0123] {Thermoplastic resin for molding (D1)} As the binder resin (D), in the plastic composition, it is preferable to include a molding thermoplastic resin (D1). The molding thermoplastic resin (D1) is not particularly limited, but is preferably a resin having partial crystallinity. For example, it may be a homopolymer or copolymer using ethylene, propylene, butylene, styrene, or the like as a monomer component. More specifically, it may be a polyolefin resin such as polyethylene, polypropylene, polybutylene, or the like, such as high density polyethylene (HDPE), linear low density polyethylene (L-LDPE), low density polyethylene (LDPE), or the like. Other useful specific examples of resins include polyester resins such as polyethylene terephthalate, polyamide resins such as nylon 6 and nylon 66, polystyrene resins, thermoplastic ionomer resins, and the like.

[0124] The resin preferably includes at least one of a polyolefin resin and a polyester resin. The resin preferably includes at least a polyolefin resin. When a polyolefin resin is used, the composition tends to have a more significant effect in improving the properties of dispersibility, weather resistance, light resistance, and heat resistance.

[0125] The thermoplastic resin for molding (D1) 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 with a differential scanning calorimeter, a thermogravimetric differential thermal analyzer, or the like.

[0126] The binder resin (D) can be used alone or in combination of two or more kinds.

[0127] {thermosetting compound} In the present invention, it is preferable to further include a thermosetting compound as the binder resin (D) in combination with the thermoplastic resin. For example, when the composition of the present invention is used to prepare an optical filter, the thermosetting compound reacts during baking of the filter segment to increase the crosslink density of the coating film, thereby improving the heat resistance of the filter segment, suppressing pigment aggregation during baking of the filter segment, and suppressing the decrease in transmittance.

[0128] 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 phenolic compounds. Epoxy compounds and oxetane compounds are preferably used in the composition of the present invention.

[0129] Examples of the epoxy compound 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.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, etc.), and polycondensates of 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.

[0130] The content of the thermosetting compound is preferably 0.5 to 300 parts by mass, and more preferably 1.0 to 50 parts by mass, relative to 100 parts by mass of the dye. When an appropriate amount is used, appropriate heat resistance can be obtained.

[0131] The composition of the present invention may contain a curing agent and a curing accelerator to aid in the curing of the thermosetting compound. Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Examples of the curing accelerator include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, etc.), and the like. , 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), 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.).

[0132] The content of the curing agent and the curing accelerator is preferably, for example, 0.01 to 15 parts by mass each relative to 100 parts by mass of the thermosetting compound.

[0133] <Photopolymerizable compound> The composition of the present invention can be made into a photosensitive composition by including a photopolymerizable compound and / or a photopolymerization initiator. The photopolymerizable compound includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to produce a transparent resin.

[0134] Examples of the photopolymerizable compound 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 the 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)acrylates, and urethane acrylates, as well as (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

[0135] (Photopolymerizable compound having an acid group) The photopolymerizable compound may include a photopolymerizable compound having an acid group, such as a sulfonic acid group, a carboxyl group, or a phosphoric acid group.

[0136] Examples of photopolymerizable compounds having an acid group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates; and the like. 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.

[0137] (Photopolymerizable compound having urethane bond) The photopolymerizable compound may contain a monomer having an ethylenically unsaturated bond and a urethane bond. Examples of the 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 further reacting the alcohol with a (meth)acrylate having a hydroxyl group.

[0138] 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.

[0139] Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

[0140] The photopolymerizable compounds can be used alone or in combination of two or more kinds.

[0141] The amount of the photopolymerizable compound is preferably 1 to 50 mass %, more preferably 2 to 40 mass parts, based on 100 mass % of the nonvolatile content of the composition. When an appropriate amount is added, the curability and developability are further improved.

[0142] <Photopolymerization initiator> The photopolymerization initiator may be, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylamino)phenyl]-2-methyl-1-butanone. acetophenone compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzil dimethyl ketal; benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t-butanone) benzophenone 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, triazine-based compounds such as 2-(naphth-1-yl)-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-(4'-methoxystyryl)-6-triazine;Examples of suitable oxime ester compounds include 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; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. Among these, oxime ester compounds are preferred.

[0143] The photopolymerization initiators can be used alone or in combination of two or more kinds.

[0144] (Oxime ester compounds) In oxime ester compounds, the NO bond of the oxime is cleaved by absorbing ultraviolet light, 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 the composition is high, the ultraviolet transmittance of the coating film may decrease, resulting in a low degree of curing of the coating film, but oxime ester compounds are preferably used because they have high quantum efficiency.

[0145] Examples of the oxime ester compound include oxime ester photopolymerization initiators described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, and the like.

[0146] The content of the photopolymerization initiator is preferably 2 to 200 parts by mass, and more preferably 2 to 150 parts by mass, relative to 100 parts by mass of the dye. When an appropriate amount is added, the photocurability and developability are further improved.

[0147] <Sensitizer> Furthermore, the composition of the present invention may contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as 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, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. , phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine 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, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0148] 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.

[0149] More specifically, examples of the 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), "Tokushu No Futoshi Zairyo" edited by Chuzaburo Ikemori et al., and "Tokushu No Futoshi Zairyo" (CMC, 1986). In addition, a sensitizer that absorbs light from the ultraviolet to near infrared region may also be contained.

[0150] The sensitizers can be used alone or in combination of two or more kinds.

[0151] The content of the sensitizer is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator. When an appropriate amount is contained, the curability and developability are further improved.

[0152] <Thiol-based chain transfer agent> The 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 irradiation with light, and generates a thiyl radical that is not easily inhibited by oxygen, so that the resulting composition has high sensitivity.

[0153] Also preferred is a polyfunctional aliphatic thiol having two or more thiol groups bonded to an aliphatic group such as a methylene or ethylene group. More preferred is a polyfunctional aliphatic thiol having four or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and curing can be achieved from the surface of the pattern to the vicinity of the substrate.

[0154] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, ... Examples of the thiopropionate include tris(2-hydroxyethyl)trimercaptopropionic acid, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Of these, preferred are ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0155] The thiol chain transfer agents can be used alone or in combination of two or more kinds.

[0156] The content of the thiol chain transfer agent is preferably 0.1 to 20% by mass, more preferably 0.1 to 10% by mass, based on 100% by mass of the nonvolatile content of the composition. When an appropriate amount is contained, the photosensitivity and taper shape are improved, and wrinkles are less likely to occur on the coating surface.

[0157] <Polymerization inhibitor> The composition of the present invention can 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.

[0158] 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, and 2-n- alkyl resorcinol compounds such as butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, and 4-tert-butyl resorcinol; alkyl hydroquinone compounds such as methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, tert-butyl hydroquinone, and 2,5-di-tert-butyl hydroquinone; phosphine compounds such as tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, and tribenzyl phosphine; phosphine oxide compounds such as trioctyl phosphine oxide and triphenyl phosphine oxide; phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite; pyrogallol; and phloroglucine.

[0159] The content of the polymerization inhibitor is preferably 0.01 to 0.4% by mass based on 100% by mass of the nonvolatile content of the composition. Within this range, the effect of the polymerization inhibitor is increased, and the linearity of the taper, wrinkles in the coating, pattern resolution, etc. are improved.

[0160] <Ultraviolet absorbing agent> The composition of the present invention may contain an ultraviolet absorbing agent, such as a benzotriazole-based compound, a triazine-based compound, a benzophenone-based compound, a cyanoacrylate-based compound, or a salicylate-based compound.

[0161] 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. This allows a high degree of compatibility between photosensitivity and resolution. When the composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

[0162] 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 composition. If the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above, adhesion may be weakened and pixel peeling may occur, whereas if it is more than the above, the sensitivity may become excessively high and the resolution may deteriorate.

[0163] 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, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl esters. mixture of 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, reaction products of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2 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-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl) 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, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, etc. In addition, oligomer type and polymer type compounds having a benzotriazole structure can also be used.

[0164] 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-triazine-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 the compound 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. In addition, oligomer and polymer type compounds having a triazine structure can also be used.

[0165] Benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

[0166] Examples of the salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

[0167] <Antioxidants> The composition of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator or thermosetting compound contained in the composition from oxidizing and yellowing due to the thermal process during thermal curing or ITO annealing, thereby improving the transmittance of the coating. In particular, when the dye concentration of the composition is high, the amount of the coating crosslinking component is reduced, so that measures such as using a highly sensitive crosslinking component or increasing the amount of the photopolymerization initiator are taken, resulting in a phenomenon in which yellowing during the thermal process becomes stronger. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a coating with high transmittance can be obtained.

[0168] Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds, etc. In the present invention, the antioxidant is preferably a compound that does not contain a halogen atom.

[0169] Among these, from the viewpoint of achieving both the transmittance and sensitivity of the coating, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0170] The antioxidants can be used alone or in combination of two or more kinds.

[0171] 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 composition, good transmittance, spectral characteristics, and sensitivity are obtained, which is more preferable.

[0172] <Amine compounds> The composition of the present invention may contain an amine compound for reducing dissolved oxygen. Examples of the amine compound 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.

[0173] <Leveling agent> The composition of the present invention may contain a leveling agent to improve the leveling property of the composition during coating. The leveling agent is preferably, for example, dimethylsiloxane having a polyether structure or 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-333 manufactured by BYK-Chemie Co., Ltd. Examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie Co., Ltd. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane 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 in 100% by mass of the non-volatile content of the composition.

[0174] The leveling agent is, for example, a type of so-called 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. As the leveling agent, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit is, for example, a polyethylene oxide unit or a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

[0175] The bonding form of the polyalkylene oxide unit with the dimethylpolysiloxane may be any of a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethylpolysiloxane, a terminal modified type in which the polyalkylene oxide unit is bonded to the terminal of the dimethylpolysiloxane, and a linear block copolymer type in which the polyalkylene oxide unit is 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.

[0176] The leveling agent may contain an anionic, cationic, nonionic or amphoteric surfactant as a supplement. Two or more types of surfactants may be mixed together.

[0177] Examples of the anionic surfactant added auxiliary to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, and the like.

[0178] Examples of cationic surfactants to be added to the leveling agent as an auxiliary include alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of nonionic surfactants to be added to the leveling agent as an auxiliary 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 dimethylamino acetate betaine, amphoteric surfactants such as alkyl imidazolines, and fluorine-based and silicon-based surfactants.

[0179] <Storage stabilizer> The 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 may be used in an amount of 0.1 to 10% by mass in 100% by mass of the pigment.

[0180] <Adhesion improver> The composition of the present invention may contain an adhesion improver such as a silane coupling agent in order to improve adhesion to the substrate. The improved adhesion due to the adhesion improver improves the reproducibility of fine lines and improves resolution.

[0181] Examples of the adhesion improver include vinyl silanes such as vinyl trimethoxy silane and vinyl triethoxy silane, (meth)acrylic silanes such as 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, 3-methacryloxypropyl triethoxy silane and 3-acryloxypropyl trimethoxy silane, epoxy silanes such as 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl methyl diethoxy silane and 3-glycidoxypropyl triethoxy silane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxy silane 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 hydrochloride salt of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureidos 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 parts by mass, preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the dye in the composition. Within this range, the effect is large, and a good balance of adhesion, resolution, and sensitivity is achieved, which is more preferable.

[0182] <Organic solvent> The composition of the present invention contains an organic solvent, which makes it easier to adjust the viscosity of the composition.

[0183] Examples of the organic solvent include ethyl lactate, butyl lactate, benzyl alcohol, chloroform, 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, 3-ethoxyethyl propionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butan ... -3-Methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, 1,8-diiodooctane, toluene, 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, 1-chlorobenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl Benzene, 1-chloronaphthalene, 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, cyclopentanone, 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, 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, dibasic acid esters, etc.,

[0184] 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 more and 180° C. or less. 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, cyclopentanone, 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.

[0185] <Removal of large particles> The composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or membrane filter, etc. In this way, it is preferable that the composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

[0186] <Water content in the composition> The 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 composition.

[0187] When the water content is within the above range, the composition has excellent dispersion stability and sensitivity even after storage over time.

[0188] The water content is preferably 1.8% by mass or less, more preferably 1.6% by mass or less, based on the total amount of the composition. If the water content is sufficiently low within this range, problems are unlikely to occur in the dispersion stability and sensitivity of the composition even after storage over time.

[0189] 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 composition while blowing in a dry inert gas, a method for dehydrating the composition by adding molecular sieves after the composition is produced, etc. are included. Among these, the method for producing the composition while blowing in a dry inert gas is preferred.

[0190] The water content can be measured by a known method such as the Karl Fischer method.

[0191] <Specific metal atoms> The composition of the present invention may contain small amounts of metal components including Li, Na, Mg, K, Cs, Co, Ca, Fe, Si and Zr (hereinafter also referred to as specific metal atoms) in addition to the dye components. If a large amount of metal components including these specific metal atoms are present, storage stability may be impaired, heat resistance may decrease, or sensitivity may decrease when prepared in the form of a photosensitive composition. In addition, an optical filter produced using a composition containing a large amount of metal components including 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 composition of the present invention is preferably 1 to 1000 ppm by mass with respect to the entire composition.

[0192] The total amount of specific metal atoms contained in the composition of the present invention is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less, based on the entire composition.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 composition.If it is within the above range, it is possible to obtain a composition that can form an optical filter that can suppress costs, has excellent storage stability, and generates less foreign matter.

[0193] The content of each specific metal atom in the 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 composition.

[0194] Methods for removing various raw materials contained in the composition or metal atoms that have been mixed in from the equipment during the manufacturing process include methods using water washing as described in JP 2010-83997 A, JP 2018-36521 A, JP 7-198928 A, JP 8-333521 A, JP 2009-7432 A, etc., and methods such as removing magnetic foreign matter using a magnet as described in JP 2011-48736 A, and a combination of these methods can be used as appropriate.

[0195] The content of specific metal atoms can be measured by inductively coupled plasma emission spectrometry (ICP).

[0196] <Toluene amount> The composition of the present invention may contain toluene, and when it does contain toluene, the content of toluene is preferably 0.1 to 10 ppm by mass. The upper limit of the toluene content is preferably 9 ppm by mass or less, more preferably 8 ppm by mass or less, and even more preferably 7 ppm by mass or less. The lower limit is preferably 0.2 ppm by mass or more, more preferably 0.3 ppm by mass or more, and even more preferably 0.4 ppm by mass or more.

[0197] <Method of producing the composition> The composition of the present invention can be prepared by mixing the above-mentioned components. In the preparation, the components may be mixed at once, or may be mixed successively after dissolving or dispersing the components in an organic solvent. For example, a dye, a derivative (B), a resin-type dispersant (C), a binder resin (D), an organic solvent, etc. are added and a dispersion treatment is performed. Then, a photopolymerizable compound, a photopolymerization initiator, etc. are mixed and mixed as necessary to produce the composition. The timing of mixing the components is arbitrary. The dispersion treatment can also be performed multiple times.

[0198] Examples of dispersing machines for carrying out the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

[0199] The average dispersed particle size (secondary particle size) of the particles in the composition is preferably 30 to 200 nm, more preferably 40 to 200 nm. If the particles have an appropriate particle size, a composition with high dispersion stability is easily obtained.

[0200] The average dispersed particle size (secondary particle size) is measured, for example, using Nikkiso Microtrack UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape set to non-spherical, and D50 particle size set to average size. The dilution solvent used for measurement is the organic solvent used for dispersion, and it is preferable to measure samples treated with ultrasound immediately after sample preparation, as this tends to give results with less variation.

[0201] The composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation, filtration with a sintered filter or membrane filter, etc. The composition of the present invention is preferably substantially free of particles of 0.5 μm or more, and more preferably free of particles of 0.3 μm or less.

[0202] <Coating> The composition of the present invention can be used for optical filters and the like by forming a coating (hereinafter also referred to as a film or coating). The coating may be used in a state in which it is laminated on a substrate, or the coating may be peeled off from the substrate. The coating may be either a flat film or a patterned coating, but a patterned coating is preferred.

[0203] (Method of producing the coating) The method for producing the coating film is not particularly limited, and any known method can be used. For example, the coating film can be produced by applying the composition of the present invention onto a substrate.

[0204] The substrate may be, for example, a substrate made of a material such as glass, resin, or silicon. An organic light-emitting layer may be formed on the substrate. An imaging element such as a CCD or CMOS may be formed on the substrate. If necessary, an undercoat layer may be provided on the substrate to improve adhesion with an upper layer, prevent diffusion of substances, and flatten the substrate surface.

[0205] The coating method may be a known method, such as a dropping method, a slit coating method, a spray method, a roll coating method, a spin coating method, a casting coating method, an inkjet method, flexographic printing, screen printing, gravure printing, or offset printing.

[0206] The thickness of the coating can be appropriately adjusted depending on the purpose, and is preferably 0.05 to 20.0 μm, more preferably 0.3 to 10.0 μm.

[0207] Next, a pattern is formed. Examples of a method for forming a pattern include a photolithography method and a dry etching method. When the film is used as a flat film, the step of forming a pattern is not necessary, and the film is dried as necessary after coating.

[0208] The method for forming the pattern will now be described in detail.

[0209] {When forming a pattern using photolithography} When a pattern is formed by a photolithography method, a layer formed by coating the near infrared absorbing composition of the present invention on a substrate is dried (pre-baked) as necessary, and then exposed to light in a pattern through a mask (exposure step), and the unexposed parts are removed by alkaline development (development step), and the pattern is then heat-treated (post-bake step) as necessary.

[0210] [Exposure process] In the exposure step, the layer formed by coating is exposed to a specific pattern through a mask using an exposure device such as a stepper. This allows the exposed portion to be cured. Examples of active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF rays (wavelength 248 nm) and ArF (wavelength 193 nm). In addition, the exposure may be performed by continuous irradiation with light, or by repeating irradiation and pause of light in a short cycle (for example, on the order of milliseconds or less) (pulse exposure).

[0211] [Development process] Next, an alkali development process is carried out, whereby the unexposed portions of the layer are dissolved in an aqueous alkali solution, leaving only the hardened portions to obtain a patterned coating. Examples of alkaline developers include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, it suppresses roughening and peeling of the pattern and improves the remaining film rate after development. Examples of the developing method include a dipping method, a spraying method, a puddle method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0212] [Post-bake process] After development, a heat treatment (post-baking) can be carried out as necessary, which improves the resistance of the coating. The temperature is preferably 80 to 300° C. The time is preferably about 2 minutes to 1 hour. When a material with low heat resistance is used for the substrate or when an organic electroluminescence element is used as the light source, the temperature is preferably 150° C. or less, and more preferably 130° C. or less.

[0213] {When forming a pattern using dry etching} When forming a pattern by dry etching, for example, the near infrared absorbing composition of the present invention is applied onto a substrate, and the layer formed is heated and cured. Next, a patterned photoresist layer is formed on the cured film, and then the cured film is dry-etched using an etching gas with the patterned photoresist layer as a mask. For pattern formation by dry etching, the method described in JP2013-064993A can be referred to.

[0214] <Optical filters> The optical filter of the present invention has a coating film formed from the composition of the present invention. The optical filter is preferably, for example, an infrared cut filter, an infrared transmission filter, etc. The optical filter of the present invention can be produced by the same method as the above-mentioned coating film.

[0215] <Infrared cameras, infrared sensors> The infrared camera and infrared sensor of the present invention have the optical filter of the present invention. Examples of the types of infrared cameras include near-infrared cameras, surveillance cameras, vehicle-mounted cameras, medical cameras, inspection and analysis cameras, and the like, and examples of the types of infrared sensors include temperature sensors, distance sensors, medical sensors, touch sensors such as displays, biometric authentication sensors, and the like. The configuration of the infrared camera and infrared sensor is not particularly limited as long as it has the optical filter of the present invention and functions as an infrared camera and an infrared sensor.

[0216] <Solid-state imaging element> The solid-state imaging element of the present invention has the optical filter of the present invention. The form of the optical filter used in the solid-state imaging element is not particularly limited, but for example, the optical filter has a plurality of photodiodes constituting a light receiving area of ​​a solid-state imaging element (CCD image sensor, CMOS image sensor, etc.) on a substrate, a transfer electrode made of polysilicon or the like, a light-shielding film with only the light receiving part of the photodiode open on the photodiode and the transfer electrode, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light receiving part of the photodiode, and a filter on the device protection film. Furthermore, the optical filter may have a configuration in which a light-collecting means (e.g., a microlens, etc., the same below) is provided on the device protection film and below the filter (the side closer to the substrate), or a configuration in which a light-collecting means is provided on the filter. The filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned, for example, in a lattice shape by partition walls. In this case, the partition walls preferably have a low refractive index with respect to each color pixel. An imaging device including a solid-state imaging element of the present invention can be used for various purposes, such as digital cameras, electronic devices with imaging functions (smartphones, tablet terminals, etc.), vehicle-mounted cameras, surveillance cameras, and infrared sensors.

[0217] <Laminate> The laminate of the present invention comprises a layer containing the composition of the present invention and at least one other layer, and can be used, for example, as an infrared transmission filter.

[0218] The thickness of the laminate is preferably 1 to 5 μm, and the thickness of each layer is preferably 0.5 to 4 μm.

[0219] The order of layers in the laminate is not particularly limited, and the laminate may further include a second layer and a third layer.

[0220] <Composition for plastics> The composition of the present invention can be suitably used as a composition for plastics. A composition for plastics is required to have durability such that it does not discolor even after being heated at a high temperature of, for example, 300° C. In contrast, the composition for plastics of the present invention can easily obtain excellent heat resistance.

[0221] The composition for plastics may be in the form of pellets called a so-called master batch or color chips, which contain a high concentration of the isoindoline compound (A) that functions as a pigment.

[0222] The composition for plastics may further contain other additive components within the range that does not impair the desired effects and does not cause any hygienic problems. Examples of additive components include wax or derivatives thereof, heavy metal deactivators, metal soaps of alkali metals, alkaline earth metals or zinc, hydrotalcite, antistatic agents such as nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants, etc., flame retardants such as halogen-based, phosphorus-based or metal oxides, lubricants such as ethylene bis alkyl amides, antioxidants and ultraviolet absorbers, processing aids, fillers, various known additives for polymers, etc. In addition, for the purpose of adjusting the color tone, other dyes, inorganic pigments and inorganic fillers may be added as necessary.

[0223] (Inorganic pigments, inorganic fillers) Examples of inorganic pigments and inorganic fillers include natural products such as clay, baryte, mica, and talc, ferrocyanides such as Prussian blue, sulfides such as zinc sulfide, sulfates such as barium sulfate, oxides such as chromium oxide, zinc white, titanium oxide, and iron oxide, hydroxides such as aluminum hydroxide, silicates such as calcium silicate and ultramarine, carbonates such as calcium carbonate and magnesium carbonate, carbon such as carbon black and graphite, and metal powders such as aluminum powder, bronze powder, and zinc powder.

[0224] <Plastic molded products> The plastic molded article of the present invention is characterized by containing the composition for plastics of the present invention. The molding method for obtaining a plastic molded article made of a plastic composition such as color chips and a plastic molding material is not particularly limited. Examples of the molding method include blow molding, inflation molding, extrusion molding, Engel molding, vacuum molding, etc. By improving the dispersibility and heat resistance of the isoindoline compound (A) contained in the plastic colorant and the plastic molding material, it is possible to obtain a plastic molded article that does not discolor even after heating at high temperatures during molding and that maintains a desired hue well.

[0225] <<Organic semiconductor ink>> The organic semiconductor ink of the present invention contains an isobenzindoline compound (A) represented by the general formula (1) described above, a p-type organic semiconductor compound (P), an n-type organic semiconductor compound (N), and the organic solvent described above.

[0226] The isobenzindoline compound (A) represented by the general formula (1) in the organic semiconductor ink is preferably 0.2% by mass or more and 1.0% by mass or less, more preferably 0.3% by mass or more, and even more preferably 0.4% by mass or more.

[0227] From the viewpoint of coatability, the organic solvent in the organic semiconductor ink is preferably toluene, xylene, chloroform, 1-chlorobenzene, 1,8-diiodooctane, or 1-chloronaphthalene.

[0228] The organic solvent in the organic semiconductor ink can be used alone or in combination of two or more.

[0229] It is preferable to use two or more organic solvents in the organic semiconductor ink in combination, and it is preferable to mix 1,8-diiodooctane or 1-chloronaphthalene. Thereby, since the bulk heterostructure of the isobenzindoline compound (A) represented by the general formula (1), the p-type organic semiconductor compound (P), and the n-type organic semiconductor compound (N) can be stabilized, the heat resistance and light resistance can be improved.

[0230] It is preferable to add 0.5 to 5.0% by volume of 1,8-diiodooctane or 1-chloronaphthalene to the total amount of the organic solvent in the organic semiconductor ink, more preferably 1.0 to 3.0% by volume, and even more preferably 1.5 to 2.5% by volume.

[0231] <p-type organic semiconductor compound (P)> The p-type organic semiconductor compound (P) is a hole-transporting organic compound exhibiting p-type organic semiconductor properties, and examples include low-molecular compounds and high-molecular compounds. For example, rubrene derivatives, acene derivatives such as anthracene, tetracene, pentacene, heteroacene derivatives, thiophene derivatives, thiazole derivatives, triarylamine derivatives, fluorene derivatives, carbazole derivatives, phthalocyanine derivatives, subphthalocyanine derivatives, diketopyrrolopyrrole derivatives, benzodifuranone derivatives, and the like can be mentioned. In terms of specific structures, compounds having the following structures (P-1) to (P-4) can be mentioned. Note that n in the formula indicates the degree of polymerization and is a positive number. The present invention is not limited thereto.

[0232]

Chemical formula

[0233] The p-type organic semiconductor compound (P) in the organic semiconductor ink is preferably 0.4% by mass or more and 1.5% by mass or less, more preferably 0.6% by mass or more, and even more preferably 0.8% by mass or more.

[0234] <n-type organic semiconductor compound (N)> The n-type organic semiconductor compound (N) is an electron-transporting organic compound exhibiting n-type organic semiconductor properties, and examples include low-molecular compounds and high-molecular compounds. For example, fullerene derivatives, rubrene derivatives, halogenated acene derivatives such as anthracene, tetracene, pentacene, heteroacene derivatives, perylene derivatives, thiophene derivatives, thiazole derivatives, fluorene derivatives, carbazole derivatives, halogenated phthalocyanine derivatives, diketopyrrolopyrrole derivatives, benzodifuranone derivatives, and the like can be mentioned. In terms of specific structures, compounds having the following structures (N-1 to N-4) can be mentioned. Note that n in the formula indicates the degree of polymerization and is a positive number. The present invention is not limited thereto.

[0235]

Chemical formula

[0236] The content of the n-type semiconductor compound (N) in the organic semiconductor ink is preferably 0.6% by mass or more and 2.0% by mass or less, more preferably 0.8% by mass or more, and even more preferably 1.0% by mass or more.

[0237] <Coating using organic semiconductor ink> The coating film (hereinafter, also referred to as a near-infrared absorbing organic semiconductor layer) using the organic semiconductor ink of the present invention can be prepared by using, but is not limited to, a spin coating method, an inkjet method, a silk screen method, a bar coater method, a transfer method, or a spray method. From the viewpoint of simplicity, the spin coating method is preferred.

[0238] <Organic semiconductor devices> Examples of organic semiconductor devices using a coating film formed from the organic semiconductor ink of the present invention include, but are not limited to, organic field effect transistors and photoelectric conversion devices such as organic photodetectors and organic thin-film solar cells. From the viewpoint of adding the isoindoline compound (A) represented by general formula (1) having excellent heat resistance and light resistance, photoelectric conversion devices are preferred, and organic photodetectors are more preferred.

[0239] (Photoelectric conversion device) Specific examples of the photoelectric conversion device structure are shown in FIG. 1, but the present invention is not limited thereto.

[0240] Examples of electrode materials include metals such as silver, gold, platinum, copper, iron, zinc, tin, aluminum, indium, nickel, cobalt, scandium, yttrium, vanadium, indium, ytterbium, lithium, magnesium, sodium, and potassium, metal oxides such as indium, tin, molybdenum, and nickel, and composite metal oxides such as indium tin oxide (ITO), indium zinc oxide (IZO), aluminum zinc oxide (AZO), and gallium zinc oxide (GZO), but the present invention is not limited to these. It is preferable that at least one of the positive electrode and the negative electrode is transparent. It is preferable that the transparent electrode has an average transmittance of 80% or more in the visible region of 400 nm or more.

[0241] Examples of materials for the hole blocking layer and the electron blocking layer include conductive polymers such as polythiophene polymers, polyfluorene polymers, and polypyrrole polymers, and metal oxides such as graphene, molybdenum, tungsten, nickel, vanadium, zirconium, zinc, copper, and ruthenium, but the present invention is not limited to these.

[0242] <Organic photodetector> The organic semiconductor device of the present invention can be used as an organic photodetector by being provided in an infrared sensor or an image sensor. Since it contains the isoindoline compound (A) represented by the general formula (1) having near-infrared absorbing properties, it is excellent in detecting light in the near-infrared region. EXAMPLES

[0243] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these. In addition, "parts" means "parts by mass" and "%" means "% by mass".

[0244] Before describing the examples, each measurement method will be described.

[0245] (Method of Identifying Isoindoline Compound (A)) The isoindoline compound (A) of the present invention was identified by comparing the molecular ion peak of the mass spectrum with the mass number (theoretical value) obtained by calculation. The molecular ion peak of the mass spectrum was measured using Waters ACQUITY UPLC H-Class (UPLC) (column used: ACQUITY UPLC BEH C18 Column 130 Å, 1.7 μm, 2.1 mm × 50 mm) / Ms TAP XEVO TQD. Due to the nature of the measurement, the measured value is determined by the mass number of the theoretical molecular weight minus 1, since the H (proton) of the compound is eliminated.

[0246] (Maximum absorption wavelength of isoindoline compound (A) (λ max ) Measurement method) λ of isoindoline compound (A) max The measurement of λ is performed by measuring the ultraviolet-visible absorption spectrum according to the following procedure. max asked for. In an air atmosphere, the absorption spectrum of a 10 ppm solution (organic solvent: N-methyl-2-pyrrolidone, liquid temperature: 25°C) was measured in a quartz cell with an optical path length of 1 mm using a spectrophotometer in the wavelength range of 600 to 1200 nm.

[0247] (Acid value of resin-type dispersant (C) having acidic functional group and binder resin (D)) The acid values ​​of the resin-type dispersant (C) and binder resin (D) with acidic functional groups were determined by potentiometric titration using a 0.1N potassium hydroxide-ethanol solution. The acid values ​​of the resin-type dispersant and binder resin with acidic functional groups indicate the acid value of the non-volatile content.

[0248] (Weight average molecular weight (Mw) of resin-type dispersant (C) having an acidic functional group and binder resin (D)) The weight average molecular weight (Mw) of the resin-type dispersant (C) having an acidic functional group and the binder resin (D) 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.

[0249] (Weight average molecular weight (Mw) of resin-type dispersant (C) having a basic functional group) The weight average molecular weight (Mw) of the resin-type dispersant (C) having a basic functional group 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.

[0250] (Amine value of resin-type dispersant (C) having basic functional group) The amine value of the resin-type dispersant (C) having a basic functional group was determined by potentiometric titration using a 0.1N hydrochloric acid aqueous solution, and then converted into the equivalent amount of potassium hydroxide. The amine value of the resin-type dispersant having a basic functional group indicates the amine value of the non-volatile portion.

[0251] (Quaternary ammonium salt value of resin-type dispersant (C) having basic functional group) The quaternary ammonium salt value of the resin-type dispersant (C) having a basic functional group was determined by titration with 0.1N silver nitrate solution using 5% potassium chromate solution as an indicator, and then converted into the potassium hydroxide equivalent. The quaternary ammonium salt value of the resin-type dispersant having a basic functional group indicates the quaternary ammonium salt value of the non-volatile portion.

[0252] <Production of isoindoline compound (A)> [Example 1] (Isoindoline compound (A-1))

[0253] In a 1L four-neck flask equipped with a reflux condenser and a stirrer, 500 parts of N-methyl-2-pyrrolidone (NMP), 500 parts of glacial acetic acid, 20.0 parts of 3,7-dihydrobenzo[1,2-b:4,5-b']difuran-2,6-dione (BzDF), 11.5 parts of p-toluenesulfonic acid monohydrate, and 18.3 parts of diiminoisoindoline (DII) were added in this order and stirred. The mixture was heated and stirred at 120°C until the raw material benzodifuranone disappeared. The disappearance of the raw material was confirmed by ultra-performance high-resolution liquid chromatography (UPLC). The reaction slurry was filtered using a Buchner funnel to obtain a solid content. The solid content was dried in a hot air dryer at 80°C to obtain 45.5 parts of isoindoline compound (A-1) (yield 58%). The maximum absorption wavelength was 801 nm. The theoretical molecular weight of the isoindoline compound (A-1) was 749.65, whereas the measured molecular weight was 748.65.

[0254] Isoindoline Compound (A-1) [ka]

[0255] [Example 2] (Isoindoline compound (A-2)) Except for changing 20.0 parts of BzDF, 11.5 parts of p-toluenesulfonic acid monohydrate, and 18.3 parts of DII to 20 parts of 3,7-dihydrobenzo[1,2-b:4,5-b']dithiophene-2,6-dithione, 8.6 parts of p-toluenesulfonic acid monohydrate, and 13.7 parts of DII, the same operation as for isoindoline compound (A-1) was performed to obtain 49.1 parts of isoindoline compound (A-2) (yield 70%). The maximum absorption wavelength was 805 nm. The theoretical molecular weight of isoindoline compound (A-2) was 894.20, while the measured value was 893.01.

[0256] Isoindoline compound (A-2) [ka]

[0257] [Example 3] (Isoindoline compound (A-3)) In a 1L beaker, 800 parts of water, 100 parts of 28% aqueous ammonia, 50 parts of diiminoisoindoline, and 25.0 parts of malononitrile (raw material: a'-3) were added in this order and stirred. The mixture was heated and stirred at 40°C until the raw material diiminoisoindoline disappeared. The disappearance of the raw material was confirmed by ultra-performance high-resolution liquid chromatography (UPLC). The reaction slurry was filtered using a Buchner funnel and dried in a hot air dryer at 80°C to obtain 47.2 parts of intermediate (a-3) (yield 71%). The theoretical molecular weight of intermediate (a-3) was 193.43, compared to 194.20.

[0258] Intermediate (a-3) [ka]

[0259] Next, 10.0 parts of BzDF, 300 parts of glacial acetic acid, 5.8 parts of p-toluenesulfonic acid, and 42.9 parts of intermediate (a-3) were added in this order to a 1 L four-neck flask equipped with a reflux condenser and a stirrer, and stirred. The mixture was heated and stirred under reflux until the raw material BzDF disappeared. The disappearance of the raw material was confirmed by ultra-performance high-resolution liquid chromatography (UPLC). The reaction slurry was filtered using a Buchner funnel and dried in a hot air dryer at 80°C to obtain 34.3 parts of isoindoline compound (A-3) (yield 60%). The maximum absorption wavelength was 730 nm. The theoretical molecular weight of the isoindoline compound (A-3) was 544.49, while the measured value was 543.53.

[0260] Isoindoline Compound (A-3) [ka]

[0261] [Examples 3 to 16, 19] (Isoindoline compounds (A-4) to (A-16), (A-19)) Isoindoline compounds (A-4) to (A-16) and (A-19) were obtained in the same manner as isoindoline compound (A-3), except for changing the composition shown in Table 1. In addition, the measured values ​​of isoindoline compounds (A-4) to (A-16) and (A-19) by mass spectrometry using UPLC were values ​​of the mass number of the theoretical molecular weight minus 1.

[0262] [Example 17] (Isoindoline compound (A-17)) 50 parts of isoindoline compound (A-10), 500 parts of sodium chloride, and 60 parts of diethylene glycol were charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 60° C. Next, the kneaded mixture was poured into warm water, heated to about 80° C. and stirred for 1 hour to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, then dried overnight at 80° C. and pulverized to obtain 47.5 parts of finely divided isoindoline compound (A-17).

[0263] [Example 18] (Isoindoline compound (A-18)) Except for changing 50 parts of the isoindoline compound (A-10) to 50 parts of the isoindoline compound (A-13), 46.9 parts of finely divided isoindoline compound (A-18) was obtained in the same manner as in the production of the isoindoline compound (A-17).

[0264] [Example 20] (Isoindoline compound (A-20)) 27.2 parts of isoindoline compound (A-20) was obtained in the same manner as isoindoline compound (A-3), except that 25.0 parts of malononitrile (raw material: a'-3) and 10.0 parts of BzDF were replaced with 61.1 parts of 1-ethylindolin-2-one and 10.0 parts of benzo[1,2-b:4,5-b']dipyrrole-2,6(1H,3H)-dione. The theoretical molecular weight of isoindoline compound (A-20) was 901.12, while the measured value was 899.98.

[0265] Isoindoline Compounds (A-20) [ka]

[0266] [Table 1]

[0267] [ka]

[0268] [ka]

[0269] [ka]

[0270] [ka]

[0271] [Comparative Examples 1 to 3] (Comparative example compound (Z-1)) Comparative Example Compound (Z-1) was prepared with reference to JP2015-172102A.

[0272] Comparative example compound (Z-1) [ka]

[0273] (Comparative example compound (Z-2)) Comparative Example Compound (Z-2) was prepared with reference to JP-A-2007-92060.

[0274] Comparative example compound (Z-2) [ka]

[0275] (Comparative example compound (Z-3) Comparative example compound (Z-3) was prepared with reference to JP 2021-177243 A.

[0276] Comparative example compound (Z-3) [ka] <Production of Resin-Type Dispersant (C)> (Resin-type dispersant (C-1)) In a reaction vessel equipped with a stirrer and a thermometer, 60 parts of 2-isocyanatoethyl methacrylate, 29 parts of 3-(dimethylamino)propylamine, and 120 parts of THF were charged and stirred at room temperature for 5 hours. After confirming that the reaction was complete by FT-IR, the solvent was distilled off with a rotary evaporator to obtain 73 parts of the following monomer (c-1) as a pale yellow transparent liquid (yield 82%). The obtained compound was identified by 1H-NMR.

[0277] Monomer (c-1) [ka]

[0278] In a reaction vessel equipped with a stirrer and a thermometer, 6.6 parts of monomer (c-1) and 5 parts of ion-exchanged water were charged, and after stirring at room temperature, 8 parts of 35% aqueous hydrochloric acid solution were added dropwise. The completion of the reaction was confirmed by amine value measurement, and 20 parts of aqueous solution of monomer (c-2) was obtained as a pale yellow transparent liquid. The obtained compound was identified by 1H-NMR.

[0279] Monomer (c-2) [ka]

[0280] In a reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 17.7 parts of methyl methacrylate, 53.2 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 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 polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Next, 20 parts of PGMAc, 21.2 parts of monomer (c-1) as the second block monomer, and 27 parts of an aqueous solution of monomer (c-2) (non-volatile content 38%) were added to the reaction tank, and the reaction was continued by stirring while maintaining the temperature at 110°C under a nitrogen atmosphere. After 2 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate of the second block was 98% or more based on the non-volatile content. The reaction solution was then cooled to room temperature to terminate the polymerization. PGMAc was added to the block copolymer solution synthesized above so that the non-volatile content was 40% by mass. In this way, a resin-type dispersant (C-1) was obtained with an amine value per non-volatile content of 50 mgKOH / g, a quaternary ammonium salt value of 20 mgKOH / g, a weight average molecular weight (Mw) of 9,800, and a non-volatile content of 40% by mass.

[0281] (Resin-type dispersant (C-2)) In a reaction apparatus equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was replaced 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 polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Next, 61 parts of PGMAc and 20 parts of dimethylaminoethyl methacrylate (hereinafter referred to as DM) as a second block monomer were added to this reactor, and the reaction was continued by stirring while maintaining 110°C under a nitrogen atmosphere. Two hours after the addition of dimethylaminoethyl methacrylate, a sample was taken from the polymerization solution and the non-volatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more based on the non-volatile 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 non-volatile content was 40% by mass. In this way, a resin-type dispersant (C-2) was obtained that had an amine value of 71.4 mgKOH / g per non-volatile content, a weight average molecular weight of 9900 (Mw), a non-volatile content of 40% by mass, a poly(meth)acrylate skeleton, and a tertiary amino group.

[0282] (Resin-type dispersant (C-3)) In a reaction apparatus equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was replaced 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 polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Next, 61 parts of PGMAc and 25.6 parts of an aqueous solution of methacryloyloxyethyl trimethyl ammonium chloride ("Acryester DMC78" manufactured by Mitsubishi Rayon Co., Ltd.) as a second block monomer were added to the reactor, and the reaction was continued by stirring while maintaining 110°C under a nitrogen atmosphere. Two hours after adding the methacryloyloxyethyl trimethyl ammonium chloride, a sample of the polymerization solution was taken and the non-volatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more based on the non-volatile 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 non-volatile content was 40% by mass. In this way, a resin-type dispersant (C-3) was obtained, which has a quaternary ammonium salt value per non-volatile content of 29.4 mg KOH / g, a weight average molecular weight of 9800 (Mw), and a poly(meth)acrylate skeleton with a non-volatile content of 40% by mass.

[0283] (Resin-type dispersant (C-4)) In a reaction vessel equipped with a stirrer and a thermometer, 55 parts of 4-dimethylamino-1,2-epoxybutane and 120 parts of tetrahydrofuran (THF) were charged, and the mixture was heated and stirred at 70°C, and 35 parts of methacrylic acid were added dropwise over 60 minutes. After the completion of the dropwise addition, the mixture was heated and stirred at 70°C for another 2 hours, and the reaction was confirmed to be complete by 1H-NMR, and then the mixture was allowed to cool to room temperature. The reaction solution was washed successively with 300 parts of ion-exchanged water, 200 parts of saturated sodium bicarbonate, and 200 parts of saturated saline, and then 20 g of magnesium sulfate was added to the organic layer, stirred, and filtered. The solvent of the obtained solution was distilled off with a rotary evaporator, and 31 parts of the following structure-containing monomer (c-4) was obtained as a pale yellow transparent liquid (yield 42%). The obtained compound was identified by 1H-NMR.

[0284] Monomer (c-4) [ka]

[0285] In a reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 17.6 parts of methyl methacrylate, 52.8 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 2.6 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 100 parts of propylene glycol monomethyl ether acetate were charged, and the temperature was raised to 110°C under a nitrogen stream to initiate polymerization of the first block. After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Next, 25 parts of PGMAc and 25.1 parts of monomer (c-4) as the second block monomer were added to the reaction tank, and the reaction was continued by stirring while maintaining the temperature at 110°C under a nitrogen atmosphere. Two hours after adding monomer (c-4), a sample was taken from the polymerization solution and the non-volatile content was measured. It was confirmed that the polymerization conversion rate of the second block was 98% or more, calculated from the non-volatile content. Further, 4.5 parts of benzyl chloride was added to the reaction vessel, 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 so that the non-volatile content was 40% by mass. In this way, a resin-type dispersant (C-4) was obtained with an amine value per non-volatile content of 50 mgKOH / g, a quaternary ammonium salt value of 20 mgKOH / g, a weight average molecular weight (Mw) of 9,800, and a non-volatile content of 40% by mass.

[0286] (Resin-type dispersant (C-5)) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 50 parts of methyl methacrylate, 50 parts of n-butyl methacrylate, and 45.4 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 70°C, 6 parts of 3-mercapto-1,2-propanediol were added, and 0.12 parts of AIBN (azobisisobutyronitrile) were further added, and the reaction was carried out for 12 hours. It was confirmed that 95% had reacted by measuring the non-volatile content. Next, 9.7 parts of pyromellitic anhydride, 70.3 parts of PGMAc, and 0.20 parts of DBU (1,8-diazabicyclo-[5.4.0]-7-undecene) as a catalyst were added, and the reaction was carried out at 120°C for 7 hours. It was confirmed that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and the reaction was terminated. PGMAc was added to adjust the non-volatile content to 40%. In this way, a resin-type dispersant (C-5) having an acid value of 43, a weight average molecular weight of 9000, a poly(meth)acrylate skeleton, and an aromatic carboxyl group was obtained.

[0287] (Resin-type dispersant (C-6)) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic anhydride, 0.01 parts of monobutyltin oxide, and 88.9 parts of PGMAc were charged and replaced with nitrogen gas. The reaction vessel was heated to 100°C and reacted for 7 hours. After confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, the temperature in the system was cooled to 70°C, 50 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, and 20 parts of hydroxymethyl methacrylate were charged, and 0.12 parts of AIBN and 26.8 parts of PGMAc were added and reacted for 10 hours. The reaction was terminated when it was confirmed that the polymerization had progressed to 95% by measuring the non-volatile content. PGMAc was added to adjust the nonvolatile content to 40%, to obtain a resin-type dispersant (C-6) with an acid value of 43, a weight average molecular weight of 9000, a poly(meth)acrylate skeleton, and aromatic carboxyl groups.

[0288] (Resin-type dispersant (C-7)) PGMAc was added to BYK-P104 (manufactured by BYK Japan) to adjust the non-volatile content to 40%.

[0289] (Resin-type dispersant (C-8)) PGMAc was added to Disperbyk-171 (manufactured by BYK Japan) to adjust the non-volatile content to 40%.

[0290] (Resin-type dispersant (C-9)) PGMAc was added to Disperbyk-142 (manufactured by BYK Japan) to adjust the non-volatile content to 40%.

[0291] (Resin-type dispersant (C-10)) 40% non-volatile PGMAc solution of the following copolymer

[0292] Resin-type dispersant (C-10) [ka]

[0293] <Production of binder resin (D)> (Binder resin (D-1)) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer. 70.0 g of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C and replaced with nitrogen in the reaction vessel. 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 g of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 0.4 g of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours from the dropping tube. After the dropping was completed, the reaction was continued for another 3 hours, and a solution of an acrylic resin with a weight average molecular weight (Mw) of 26,000 was obtained. After cooling to room temperature, about 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 previously synthesized resin solution so that the non-volatile content was 20 mass % to prepare a binder resin (D-1).

[0294] (Binder resin (D-2)) A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 370g of cyclohexanone, heated to 80°C and substituted with nitrogen in the flask, and then a mixture of 18g of dicyclopentanyl methacrylate, 10g of benzyl methacrylate, 18.2g of glycidyl methacrylate, 25g of methyl methacrylate and 2.0g of 2,2'-azobisisobutyronitrile was dropped from the dropping tube over 2 hours. After the dropping, the mixture was reacted at 100°C for another 3 hours, and then a solution of 1.0g of azobisisobutyronitrile in 50g of cyclohexanone was added, and the reaction was continued at 100°C for another 1 hour. Next, the inside of the container was replaced with air, and 9.3 g of acrylic acid (100% of glycidyl group) was added to 0.5 g of trisdimethylaminophenol and 0.1 g of hydroquinone. The reaction was continued for 6 hours at 120 ° C., and the reaction was terminated when the solid acid value reached 0.5, to obtain an acrylic resin solution. Furthermore, 19.5 g of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 g of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the resin solution synthesized earlier so that the non-volatile content was 20 mass% to prepare a binder resin (D-2). The weight average molecular weight (Mw) was 19,000.

[0295] (Binder resin (D-3)) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 207 g of PGMAc was charged in the reaction vessel, which was then heated to 80°C and replaced with nitrogen in the reaction vessel. From the dropping tube, a mixture of 20 g of methacrylic acid, 20 g of paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd.'s "Aronix (registered trademark) M110"), 45 g of methyl methacrylate, 8.5 g of 2-hydroxyethyl methacrylate and 1.33 g of 2,2'-azobisisobutyronitrile was dropped over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the total amount of the copolymer solution obtained was stirred while stopping the nitrogen gas and injecting dry air for 1 hour, and then cooled to room temperature, and a mixture of 6.5 g of 2-methacryloyloxyethyl isocyanate ("Karens (registered trademark) MOI" manufactured by Showa Denko K.K.), 0.08 g of dibutyltin laurate, and 26 g of PGMAc was dropped at 70 ° C. for 3 hours. After the dropwise addition was completed, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the resin solution synthesized earlier so that the non-volatile content was 20 mass% to prepare a binder resin (D-3). The weight average molecular weight (Mw) was 18,000.

[0296] <Production of Composition> [Example 101] (Composition (PP-1)) The mixture of the following composition was stirred and mixed uniformly, then dispersed in an Eiger mill using zirconia beads having a diameter of 0.5 mm for 3 hours, and then filtered through a 1.5 μm filter to prepare a composition (PP-1). Isoindoline compound (A-1) 10.0 parts Resin-type dispersant (C-1) 25.0 parts Propylene glycol monomethyl ether acetate (PGMAC) 65.0 parts

[0297] [Examples 102 to 136, Comparative Examples 101 to 103] (Composition (PP-2)~(PP-39)) Compositions (PP-2) to (PP-39) were obtained in the same manner as for composition (PP-1), except that the compositions and amounts were changed to those shown in Table 2. The derivatives (B-1) to (B-2) are derivatives (B) shown below.

[0298] [ka]

[0299] [Table 2] <Evaluation of Composition> The compositions (PP-1) to (PP-39) obtained in the examples and comparative examples were subjected to evaluation tests for heat resistance and light resistance by the following methods. The results are shown in Table 3.

[0300] (Evaluation of heat resistance) The obtained compositions (PP-1) to (PP-39) were applied onto a 1.1 mm thick glass substrate using a spin coater, adjusting the rotation speed of the spin coater so that the film thickness after post-baking would be 1.0 μm. After application, the substrate was pre-baked for 1 minute on a hot plate at 60° C., and then post-baked for 20 minutes at 230° C. to prepare a substrate. The film thickness was measured using DEKTAK. Then, the substrate was additionally heated at 260° C. for 20 minutes. The absorbance at the maximum absorption wavelength was measured in the spectrum before the additional heating and in the spectrum after the additional heating. The absorbance was measured in the wavelength range of 500 nm to 1500 nm using a spectrophotometer (U-4100, Hitachi High-Technologies Corporation). The residual ratio according to the following formula was used to evaluate heat resistance. (Residual rate) = (Absorbance after additional heating) / (Absorbance before additional heating) ○: Residual rate is 95% or more △: Residual rate is 90% or more, but less than 95% ×: Residual rate is less than 90%

[0301] (Evaluation of light resistance) The substrate was prepared in the same manner as before the additional heating for the evaluation of heat resistance, and then placed in a light resistance tester (TOYOSEIKI "SUNTEST CPS+") and left to stand for 24 hours. The absorbance was measured using a spectrophotometer (U-4100 Hitachi High-Technologies Corporation) before and after light irradiation. The remaining rate was calculated from the pre-irradiation and post-irradiation spectral values ​​using the following formula to evaluate the light resistance. 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%

[0302] [Table 3]

[0303] The results in Table 3 show that the compositions (PP-1) to (PP-36) containing the isoindoline compound (A) of the present invention were excellent in heat resistance and light resistance.

[0304] <Production of Photosensitive Composition> [Example 201] (Photosensitive composition (PR-1)) The following raw materials were mixed and stirred, and then filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive composition (PR-1). Composition (PP-1) 50.0 parts Binder resin (D-1) 7.5 parts Photopolymerization initiator (Toagosei Co., Ltd. "Aronix M-306") 2.0 parts Photopolymerization initiator (ADEKA "ADEKA Arcles NCI-831E") 1.5 parts PGMAC 39.0 copies

[0305] [Examples 202 to 236, Comparative Examples 201 to 203] Photosensitive compositions (PR-2) to (PR-39) were obtained in the same manner as in the production of photosensitive composition (PR-1), except that the compositions were changed as shown in Table 4.

[0306] <Evaluation of Photosensitive Composition> The photosensitive compositions (PR-1) to (PR-39) obtained in the examples were tested for heat resistance and light resistance by the following methods. The results are shown in Table 4.

[0307] (Evaluation of heat resistance) The obtained photosensitive compositions (PR-1) to (PR-39) were applied onto a 1.1 mm thick glass substrate using a spin coater, adjusting the rotation speed of the spin coater so that the film thickness after post-baking would be 1.0 μm. After application, the substrate was pre-baked for 1 minute on a hot plate at 60° C., and then exposed to 100 mJ / cm 2 of ultra-high pressure mercury lamp USH-200DP (manufactured by Ushio Inc.). 2 The substrate was irradiated with ultraviolet light, spray-developed with an alkaline developer consisting of a 0.2% by mass aqueous solution of sodium carbonate, and then post-baked at 230°C for 20 minutes to produce a substrate. The substrate was then additionally heated at 260°C for 20 minutes. The absorbance at the maximum absorption wavelength was measured in the spectrum before and after the additional heating. The absorbance was measured in the wavelength range of 500 nm to 1500 nm using a spectrophotometer (U-4100, Hitachi High-Technologies Corporation). The heat resistance was evaluated using the residual rate calculated using the following formula. (Residual rate) = (Absorbance after additional heating) / (Absorbance before additional heating) ○: Residual rate is 95% or more △: Residual rate is 90% or more, but less than 95% ×: Residual rate is less than 90%

[0308] (Evaluation of light resistance) The substrate was prepared in the same manner as before the additional heating for the evaluation of heat resistance, and then placed in a light resistance tester (TOYOSEIKI "SUNTEST CPS+") and left to stand for 24 hours. The absorbance was measured using a spectrophotometer (U-4100 Hitachi High-Technologies Corporation) before and after light irradiation. The remaining rate was calculated from the pre-irradiation and post-irradiation spectral values ​​using the following formula to evaluate the light resistance. 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%

[0309] [Table 4]

[0310] The results in Table 4 show that the photosensitive compositions (PR-1) to (PR-36) containing the isoindoline compound (A) of the present invention were excellent in heat resistance and light resistance, similar to the compositions (PP-1) to (PP-36).

[0311] <Manufacturing of optical filters> [Example 301] (Optical filter (F-1)) The obtained photosensitive composition (PR-4) was applied onto a 1.1 mm thick glass substrate using a spin coater, adjusting the rotation speed of the spin coater so that the film thickness after post-baking would be 1.0 μm. After application, the substrate was pre-baked for 1 minute on a hot plate at 100° C., and then pattern exposure was performed through a photomask at an exposure dose of 1000 mJ / cm2 using an ultra-high pressure mercury lamp USH-200DP (manufactured by Ushio Electric Co., Ltd.) to form a near-infrared absorption cut filter of 100 μm square. The substrate was spray-developed with an alkaline developer consisting of a 0.2 mass% aqueous sodium carbonate solution, and the uncured parts of the coating were removed to form a 400 μm×400 μm pattern. The substrate was then post-baked for 120 minutes at 100° C. to prepare a substrate.

[0312] [Examples 302 to 315] (Optical filters (F-2)~(F-15)) Hereinafter, optical filters (F-2) to (F-15) were produced in the same manner as optical filter (F-1), except that the photosensitive composition (PR-4) was changed to the photosensitive composition shown in the table.

[0313] <Evaluation of optical filters> The optical filters (F-1) to (F-15) obtained in the examples were subjected to tests for heat resistance and light resistance in the same manner as for the photosensitive composition. The results are shown in the table.

[0314] [Table 5]

[0315] The results in Table 5 show that the optical filters of Examples 301 to 315 were excellent in heat resistance and light resistance.

[0316] <Production of plastic compositions and plastic molded products> (Thermoplastic resin for molding (D1)) (D1-1) Polyester MA-2101M (polyester resin, manufactured by Unitika Ltd., crystalline resin, melting point 264°C) (D1-2) Amilan CM3001-N (polyamide resin, manufactured by Toray Industries, crystalline resin, melting point 265°C) (D1-3) Iupilon S-3000 (polycarbonate resin, manufactured by Mitsubishi Engineering Plastics Corporation, amorphous resin, glass transition temperature 145°C) (D1-4) Topas (cycloolefin resin, manufactured by Polyplastics, amorphous resin, glass transition temperature 78°C) (D1-5) APEL (cycloolefin resin, manufactured by Mitsui Chemicals, amorphous resin, glass transition temperature 135°C) (D1-6) ULTEM (Polyetherimide resin, manufactured by Saudi Basic Industries Corporation, amorphous resin, glass transition temperature 217℃)

[0317] [Example 401] (Production of Masterbatch (V-1)) One part of compound (A-10) and 99 parts of thermoplastic resin (D1-1) were fed into a twin-screw extruder (manufactured by Japan Steel Works, Ltd.) having a screw diameter of 30 mm through the same feed port, melt-kneaded at 300°C, and then cut into pellets using a pelletizer to produce a master batch (V-1).

[0318] (Forming of film (W-1)) 95 parts of the dilution resin thermoplastic resin (D1-1) was mixed with 5 parts of the obtained master batch (V-1), and the mixture was melt-mixed at a temperature of 300°C using a T-die molding machine (manufactured by Toyo Seiki Co., Ltd.) to form a film (W-1) having a thickness of 250 μm.

[0319] [Examples 402 to 428, Comparative Examples 401 to 403] Films (W-2) to (W-31) having a thickness of 250 μm were produced in the same manner as film (W-1), except that the materials shown in Table 6 were used.

[0320] <Film evaluation> The films (W-1) to (W-31) obtained in the examples and comparative examples were evaluated for heat resistance and light resistance as described below. The results are shown in Table 6.

[0321] (Evaluation of heat resistance) The obtained films (W-1) to (W-31) were additionally heated at 260° C. for 20 minutes. The absorbance at the maximum absorption wavelength was measured in the spectrum before and after the additional heating. The absorbance was measured in the wavelength range of 500 nm to 1500 nm using a spectrophotometer (U-4100, manufactured by Hitachi High-Technologies Corporation). The residual rate according to the following formula was used to evaluate the heat resistance. (Residual rate) = (Absorbance after additional heating) / (Absorbance before additional heating) ○: Residual rate is 95% or more △: Residual rate is 90% or more, but less than 95% ×: Residual rate is less than 90%

[0322] (Evaluation of light resistance) A film (W) was prepared in the same manner as before the additional heating for the evaluation of heat resistance, and then placed in a light resistance tester (TOYOSEIKI "SUNTEST CPS+") and left to stand for 24 hours. The absorbance was measured using a spectrophotometer (U-4100 Hitachi High-Technologies Corporation) before and after light irradiation. The remaining rate was calculated from the pre-irradiation and post-irradiation spectral values ​​using the following formula to evaluate the light resistance. 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%

[0323] [Table 6]

[0324] The results in Table 6 show that Examples 401 to 426 were excellent in heat resistance and light resistance.

[0325] <Manufacturing of organic semiconductor ink> [Example 501] (Organic semiconductor ink (I-1)) A mixture of the following composition was added to a mayonnaise bottle, stirred and mixed at 60° C. for 4 hours, and then filtered through a 0.5 μm filter to prepare an organic semiconductor ink (I-1). As the p-type organic semiconductor compound (P-1) and the n-type organic semiconductor compound (N-1), the compounds given as specific examples of the p-type organic semiconductor compound (P) and the n-type organic semiconductor compound (N) described above were used. Isoindoline compound (A-19) 0.04g p-type organic semiconductor compound (P-1) 0.08g n-type organic semiconductor compound (N-1) 0.12g Organic solvent 1 1-chlorobenzene 10.0mL Organic solvent 2 1,8-diiodooctane 0.2mL

[0326] [Examples 502 to 512, Comparative Examples 501 to 506] (Organic semiconductor ink (I-2)~(I-18)) Organic semiconductor inks (I-2) to (I-18) were prepared in the same manner as organic semiconductor ink (I-1), except that the compositions and amounts were changed as shown in Table 7. As the p-type organic semiconductor compounds (P-1) to (P-4) and the n-type organic semiconductor compounds (N-1) to (N-4), the compounds given as specific examples of the p-type organic semiconductor compound (P) and the n-type organic semiconductor compound (N) described above were used.

[0327] [Table 7]

[0328] <Manufacturing of organic semiconductor devices> [Example 601] (Organic semiconductor devices (J1-1)) The glass substrate with the ITO film patterned was ultrasonically cleaned with toluene, acetone, ultrapure water, and isopropyl alcohol for 20 minutes each, and then placed in a plasma cleaner to clean the substrate surface for 20 minutes. Next, after irradiating with ozone UV for 30 minutes, a PEDOT:PSS thin film was formed as an electron blocking layer with a thickness of 60 nm using a spin coater, and then heat-treated at 120°C for 30 minutes. Next, the organic semiconductor ink (I-1) was applied by a spin coater so as to give a coating thickness of 100 nm, and heat-treated at 150° C. for 10 minutes to form a near-infrared absorbing organic semiconductor layer, thereby obtaining a laminate. Then, using a small high vacuum deposition apparatus, the prepared laminate was placed on a mask in the high vacuum deposition apparatus, and Ca (20 nm) as a hole blocking layer and an Al layer (80 nm) as a positive electrode were sequentially deposited to prepare an organic semiconductor device (J1-1).

[0329] [Examples 602 to 612, Comparative Examples 601 to 606] (Organic Semiconductor Devices (J1-2)~(J1-18)) Thereafter, organic semiconductor devices (J1-2) to (J1-18) were produced in the same manner as the organic semiconductor device (J-1), except that the organic semiconductor ink was changed to the composition shown in Table 8.

[0330] [Example 701] (Organic semiconductor devices (J2-1)) The glass substrate with the ITO film patterned was ultrasonically cleaned with toluene, acetone, ultrapure water, and isopropyl alcohol for 20 minutes each, then placed in a plasma cleaner and the substrate surface was cleaned with plasma for 20 minutes. Next, after irradiating with ozone UV for 30 minutes, a hole blocking layer was formed with Avantama-N10 (ZnO, 2.5wt% isopropanol dispersion) to a thickness of 60nm using a spin coater, and heat-treated at 90℃ for 30 minutes. Next, the organic semiconductor ink (I-1) was applied by a spin coater so as to give a coating thickness of 100 nm, and heat-treated at 150° C. for 10 minutes to form a near-infrared absorbing organic semiconductor layer, thereby obtaining a laminate. Thereafter, the laminate was placed on a mask in a small high vacuum deposition apparatus, and MoO was deposited as an electron blocking layer. 3 A layer of 10 nm and a layer of Au (80 nm) as a negative electrode were then sequentially formed on the cathode to prepare an organic semiconductor device (J2-1).

[0331] [Examples 702 to 712, Comparative Examples 701 to 706] (Organic Semiconductor Devices (J2-2)~(J2-18)) Hereinafter, organic semiconductor devices (J2-2) to (J2-18) were produced in the same manner as the organic semiconductor device (J2-1), except that the organic semiconductor ink was changed to the composition shown in Table 8.

[0332] <Evaluation of organic semiconductor devices as photodetectors> The organic semiconductor devices (J1-1) to (J1-18) and (J2-1) to (J2-18) obtained in the Examples and Comparative Examples were subjected to evaluation tests for heat resistance and light resistance by the following methods. The results are shown in Table 8.

[0333] (Evaluation of heat resistance) The obtained organic semiconductor devices (J1-1) to (J1-18) and (J2-1) to (J2-18) were used as photoelectric conversion elements, and the current-voltage was measured. The external quantum efficiency (EQE) at 940 nm was measured when a bias of 1 V was applied. Furthermore, as a heat resistance test for the obtained organic semiconductor devices (J1-1) to (J1-18) and (J2-1) to (J2-18), the devices were additionally heated at 260°C for 20 minutes, and then the EQE was measured. From the EQE values ​​before and after this additional heating, the residual rate was calculated using the following formula, and the heat resistance was evaluated. Residual rate = (EQE after additional heating) / (EQE before additional heating) ○: Residual rate is 90% or more △: Residual rate is 85% or more, but less than 90% ×: Residual rate is less than 85%

[0334] (Evaluation of light resistance) An ultraviolet ray cut filter ("COLORED OPTICAL GLASS L38" manufactured by HOYA CORPORATION) was attached to the obtained organic semiconductor device substrate, and a light resistance tester ("SUNTESTCPS+" manufactured by TOYOSEIKI CORPORATION) was used to test the organic semiconductor device substrate at 470 W / m 2 After leaving the device exposed to ultraviolet light for 24 hours using a xenon lamp, the current-voltage was measured. The external quantum efficiency (EQE) at 940 nm was measured when a bias of 1 V was applied. The residual rate was calculated from the EQE values ​​before and after the light resistance test using the following formula to evaluate the light resistance. Residual rate = (EQE after light resistance test) / (EQE before light resistance test) ○: Residual rate is 90% or more △: Residual rate is 85% or more, but less than 90% ×: Residual rate is less than 85%

[0335] [Table 8]

[0336] The results in Table 8 show that Examples 601 to 612 and 701 to 712 were excellent in heat resistance and light resistance, regardless of the types of p-type organic semiconductor compounds and n-type organic semiconductor compounds.

Claims

1. An isoindoline compound (A) represented by the following general formula (1). General formula (1) 【Chemistry 1】 [In formula (1), X １ and X ２ represents an oxygen atom or a sulfur atom, X ３ and X ４ is an oxygen atom, a sulfur atom, or NR １０１ Represents １０１ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or an alkoxy group which may have a substituent; Y １ ~Y ８ each independently represents a hydrogen atom, a halogen atom, a nitro group, a sulfone group, an amide group, a sulfonamide group, an optionally substituted alkyl group, an optionally substituted aryl group, an optionally substituted cycloalkyl group, an optionally substituted heterocyclic group, an optionally substituted alkoxyl group, an optionally substituted aryloxy group, an optionally substituted alkylthio group, an optionally substituted arylthio group, an optionally substituted phthalimidomethyl group, or an optionally substituted sulfamoyl group, * １ and * ２ are each independently an oxygen atom, C(CN) ２ , represents a bond to general formula (2), general formula (3), or general formula (4). General formula (2) 【Chemistry 2】 [In formula (2), X represents -O- or -NH-; R １ represents an alkyl group or an aryl group. * represents a bonding site with general formula (1). General formula (3) 【Chemistry 3】 [In formula (3), R ２ ~R ６ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, or an aryl group which may have a substituent. * represents a bonding site with general formula (1). General formula (4) 【Chemistry 4】 [In formula (4), Z represents a ring structure, When Z has multiple substituents, the multiple substituents may be the same or different. * represents a bonding site with general formula (1).

2. A composition comprising the isoindoline compound (A) according to claim 1 and a resin.

3. The composition of claim 2 further comprising an organic solvent.

4. The composition according to claim 3 , further comprising a photopolymerizable compound and / or a photopolymerization initiator.

5. An optical filter having a coating formed from the composition according to claim 3.

6. An infrared camera comprising the optical filter according to claim 5.

7. A solid-state imaging device comprising the optical filter according to claim 5 .

8. An infrared sensor comprising the optical filter according to claim 5 .

9. A laminate comprising the composition of claim 3.

10. A composition for plastics comprising the composition of claim 2.

11. A plastic molded article comprising the plastic composition according to claim 10.

12. An organic semiconductor ink comprising the isoindoline compound (A) according to claim 1, a p-type organic semiconductor compound (P), an n-type organic semiconductor compound (N), and an organic solvent.

13. A coating formed from the organic semiconductor ink according to claim 12.

14. An organic semiconductor device comprising the coating of claim 13.

15. An organic semiconductor device, wherein the photoelectric conversion layer is the coating according to claim 13.

16. An organic photodetector using the organic semiconductor device according to claim 15.

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