Method for manufacturing films, method for manufacturing optical filters, and compounds for vacuum deposition

Abstract

To provide a method for manufacturing a thin film that exhibits excellent optical properties and in-plane uniformity, and in which the difference between the wavelength at which absorbance is minimum in the visible light region and the wavelength at which absorbance is maximum in the near-infrared region is small. [Solution] A method for producing a film, comprising forming a film of a compound represented by general formula (I) by vacuum deposition, and a compound represented by general formula (I) used for film formation by vacuum deposition. Details of the substituents in general formula (I) are shown in the specification. JPEG2026046386000018.jpg39164

Description

[Technical Field]

[0001] This invention relates to a method for manufacturing a film, a method for manufacturing an optical filter, and a compound for vacuum deposition. [Background technology]

[0002] Solid-state imaging devices such as video cameras, digital still cameras, and mobile phones with camera functions use CCD or CMOS image sensors, which are solid-state image elements for color images. These solid-state image elements use silicon photodiodes in their light-receiving section that are sensitive to near-infrared light, which is imperceptible to the human eye. These solid-state image elements require luminous sensitivity correction to produce natural-looking colors, and optical filters (such as near-infrared cut filters) that selectively transmit or cut light in a specific wavelength range are often used.

[0003] Such near-infrared cut filters have traditionally been manufactured using various methods. Furthermore, Patent Documents 1 to 4 disclose photoelectric conversion elements containing squarylium dye or naphthalocyanine dye. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2008-308602 [Patent Document 2] Japanese Patent Application Publication No. 03-186251 [Patent Document 3] Japanese Patent Publication No. 2000-082583 [Patent Document 4] Japanese Patent Publication No. 2020-083866 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, with cameras becoming increasingly miniaturized in recent years, conventional filters containing dye-containing resins are becoming a hindrance to camera miniaturization due to their thickness. Optical filters containing dyes described in Patent Documents 1 to 4 do not adequately achieve the desired optical properties, and there is room for improvement, such as the thickness of the film. Furthermore, spin coating, which uses a single dye solvent, is known as a method for manufacturing thin films. In spin coating, when a single dye solvent is used at a high concentration, the optical properties of the resulting film tend to improve, but the in-plane uniformity tends to decrease. On the other hand, when a single dye solvent is used at a low concentration, the in-plane uniformity of the resulting film improves, but the optical properties tend to decrease. Therefore, the resulting film is required to achieve both good optical properties and in-plane uniformity.

[0006] The problem that one embodiment of the present invention aims to solve is to provide a method for manufacturing a thin film that has excellent optical properties and in-plane uniformity, and in which the difference between the wavelength at which absorbance is minimum in the visible light region and the wavelength at which absorbance is maximum in the near-infrared region is small. Furthermore, one embodiment of the present invention aims to solve the problem of providing a compound for vacuum deposition that produces a thin film with excellent optical properties and in-plane uniformity, and in which the difference between the wavelength at which absorbance is minimum in the visible light region and the wavelength at which absorbance is maximum in the near-infrared region is small. [Means for solving the problem]

[0007] As a result of diligent research to achieve the above objectives, the present inventors have found that a film obtained by a film manufacturing method, which includes forming a film of a compound having a specific structure as a near-infrared absorbing dye by vacuum deposition, has improved upon the shortcomings of conventional optical filters such as near-infrared cut filters. Furthermore, the resulting film is a thin film, possesses near-infrared cutting ability comparable to that of conventional near-infrared cut filters, and exhibits a high contrast in transmittance between the visible light transmission region and the near-infrared absorption region, thus completing the present invention. The means for solving the above problems include the following aspects.

[0008] <1> A method for manufacturing a film, comprising forming a film of a compound represented by the following general formula (I) by a vacuum deposition method.

[0009] [Chemical formula]

[0010] [In formula (I), R a , R b and Y satisfy the following conditions (i) or (ii). (i) A plurality of R a are independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, -L 1 or -NR e R f group (where the R [[ID=3']] e and R f each independently represent a hydrogen atom, -L a , -L b , -L c , -L d or -L e .).), A plurality of R b are independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphate group, -L 1 or -NR g R h group (where the R g and R h each independently represent a hydrogen atom, -L a , -L b E, -L c , -L d , -L e or -C(O)R i group (where the R i represents -L a , -L b , -L c , -L d or -L e ]].).).), A plurality of Y are independently -NRj R k Base (the above R j and R k Each is an independent hydrogen atom, -L a、 -L b , -L c , -L d or -L e It represents. ) represents, Said L 1 teeth, (L a ) A C1-C9 aliphatic hydrocarbon group which may have substituent L, (L b ) A halogen-substituted alkyl group having 1 to 9 carbon atoms, which may have substituent L. (L c ) A cycloaliphatic hydrocarbon group having 3 to 14 carbon atoms, which may have substituent L. (L d ) A C6-C14 aromatic hydrocarbon group which may have substituent L, (L e ) A heterocyclic group having 3 to 14 carbon atoms, which may have substituent L. (L f ) A carbon-1 to carbon-9 alkoxy group which may have a substituent L, (L g ) A carbon-1 to carbon-9 acyl group which may have a substituent L, or (L h ) A C1-C9 alkoxycarbonyl group which may have a substituent L The substituent L is at least one group selected from the group consisting of aliphatic hydrocarbon groups having 1 to 9 carbon atoms, halogen-substituted alkyl groups having 1 to 9 carbon atoms, alicyclic hydrocarbon groups having 3 to 14 carbon atoms, aromatic hydrocarbon groups having 6 to 14 carbon atoms, and heterocyclic groups having 3 to 14 carbon atoms. a ~L h It may further have at least one atom or group selected from the group consisting of halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and amino groups. (ii) at least one R bonded to one benzene ring a And, R aThe adjacent Y atoms bond to each other to form a heterocycle with 5 or 6 members containing at least one nitrogen atom, and the heterocycle may have substituents. R b and R that does not participate in the formation of the heterocycle a Each of these independently corresponds to R of condition (i) above. b and R a This is synonymous with [the above]. <2> The resulting film is an optical filter. <1> A method for manufacturing the film described above. <3> A compound used for film formation by vacuum deposition, represented by the following general formula (I).

[0011] [ka]

[0012] [In formula (I), R a , R b And Y satisfies either condition (i) or (ii) below. (i) Multiple R a These are independently hydrogen atoms, halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and -L 1 or -NR e R f Base (the above R e and R f These are, independently, hydrogen atoms and -L a , -L b , -L c , -L d or -L e It represents. ) represents, Multiple R b These are independently hydrogen atoms, halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and -L 1 or -NR g R h Base (the above R g and R h Each is an independent hydrogen atom, -L a , -L b , -L c , -L d , -L eor -C(O)R i group (where R i is -L a 、-L b 、-L c 、-L d or -L e ).), A plurality of Ys are independently -NR j R k group (where R j and R k are each independently a hydrogen atom, -L a 、-L b 、-L c 、-L d or -L e ).), Said L 1 is (L a ) an aliphatic hydrocarbon group having 1 to 9 carbon atoms which may have a substituent L, (L b ) a halogen-substituted alkyl group having 1 to 9 carbon atoms which may have a substituent L, (L c ) an alicyclic hydrocarbon group having 3 to 14 carbon atoms which may have a substituent L, (L d ) an aromatic hydrocarbon group having 6 to 14 carbon atoms which may have a substituent L, (L e ) a heterocyclic group having 3 to 14 carbon atoms which may have a substituent L, (L f ) an alkoxy group having 1 to 9 carbon atoms which may have a substituent L, (L g ) an acyl group having 1 to 9 carbon atoms which may have a substituent L, or (L h ) an alkoxycarbonyl group having 1 to 9 carbon atoms which may have a substituent L[[ID=7憨]] represents, said substituent L is at least one group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a halogen-substituted alkyl group having 1 to 9 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms and a heterocyclic group having 3 to 14 carbon atoms, said L a ~L hIt may further have at least one atom or group selected from the group consisting of halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and amino groups. (ii) at least one R bonded to one benzene ring a And, the aforementioned R a The adjacent Y and the other are bonded to each other to form a heterocycle with 5 or 6 members containing at least one nitrogen atom, and the heterocycle may have substituents. R b and R that does not participate in the formation of the heterocycle a Each of these independently corresponds to R of condition (i) above. b and R a This is synonymous with [the above]. [Effects of the Invention]

[0013] According to one embodiment of the present invention, a method for manufacturing a film is provided that yields a thin film with excellent optical properties and in-plane uniformity, and in which the difference between the wavelength at which absorbance is minimum in the visible light region and the wavelength at which absorbance is maximum in the near-infrared region is small. According to one embodiment of the present invention, a compound is provided that can be used for film formation by vacuum deposition, wherein the resulting film has excellent optical properties and in-plane uniformity, is a thin film, and has a small difference between the wavelength at which absorbance is minimum in the visible light region and the wavelength at which absorbance is maximum in the near-infrared region. [Brief explanation of the drawing]

[0014] [Figure 1] Figure 1 is a schematic diagram showing a method for measuring transmittance when measured from the vertical direction of an optical filter. [Modes for carrying out the invention]

[0015] The contents of the present invention will be described in detail below. The description of the constituent elements described below may be based on representative embodiments of the present invention, but the present invention is not limited to such embodiments. In this specification, the "~" symbol indicating a numerical range is used to mean that the numbers before and after it are included as the lower and upper limits, respectively. In this specification, a combination of two or more preferred embodiments is a more preferred embodiment. In this specification, the near-infrared region refers to the wavelength range of 700 nm to 2500 nm.

[0016] <Memory manufacturing method> The present invention relates to a method for manufacturing a film, which includes forming a film of a compound represented by general formula (I) (hereinafter sometimes referred to as "compound (I)") by vacuum deposition (hereinafter sometimes referred to as the "vacuum deposition process"). By including the vacuum deposition process, the method for manufacturing the film can produce a thin film in which the difference between the wavelength at which absorbance is minimum in the visible light region and the wavelength at which absorbance is maximum in the near-infrared region is small. In the resulting film, a small difference between the wavelength at which absorbance is minimum in the visible light region and the wavelength at which absorbance is maximum in the near-infrared region means that there is a large difference between the transmittance in the visible light region and the transmittance in the near-infrared region, and the transmittance contrast is high. The following describes in detail the method for manufacturing a film according to the present invention.

[0017] [Vacuum deposition process] The vacuum deposition process involves forming a film of compound (I) by vacuum deposition, and more preferably, the film is formed by vacuum deposition of compound (I) onto a substrate, which will be described later.

[0018] <Compound represented by formula (I)> The compound represented by the following formula (I) used in the film manufacturing method according to the present invention is a squarylium-based compound. From the viewpoint of obtaining a thin film in which the difference between the wavelength at which absorbance is minimum in the visible light region and the wavelength at which absorbance is maximum in the near-infrared region is small, compound (I) is suitable for film formation by vacuum deposition.

[0019] [ka]

[0020] In formula (I), R a , R b And Y satisfies either condition (i) or (ii) below. <<Condition (i)>> In equation (I), there are multiple R a These are independently hydrogen atoms, halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and -L 1 or -NR e R f Group (R e and R f Each is an independent hydrogen atom, -L a , -L b , -L c , -L d or -L e It represents. ) represents, Multiple R b These are independently hydrogen atoms, halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and -L 1 or -NR g R h Group (R g and R h Each is an independent hydrogen atom, -L a , -L b , -L c , -L d , -L e or -C(O)R i Group (R i is, -L a , -L b , -L c , -L d or -L e It represents. ) It represents. ) It represents, Multiple Ys are independently -NR j R k Group (R j and R k Each is an independent hydrogen atom, -L a , -L b , -L c , -L d or -L e It represents. ) represents, L1 teeth, (L a ) A C1-C9 aliphatic hydrocarbon group which may have substituent L, (L b ) A halogen-substituted alkyl group having 1 to 9 carbon atoms, which may have substituent L. (L c ) A cycloaliphatic hydrocarbon group having 3 to 14 carbon atoms, which may have substituent L. (L d ) A C6-C14 aromatic hydrocarbon group which may have substituent L, (L e ) A heterocyclic group having 3 to 14 carbon atoms, which may have substituent L. (L f ) A carbon-1 to carbon-9 alkoxy group which may have a substituent L, (L g ) A carbon-1 to carbon-9 acyl group which may have a substituent L, or (L h ) A C1-C9 alkoxycarbonyl group which may have a substituent L The substituent L is at least one selected from the group consisting of an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a halogen-substituted alkyl group having 1 to 9 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms. a ~L h It may further have at least one atom or group selected from the group consisting of halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and amino groups.

[0021] Said L a ~L h Preferably, the total number of carbon atoms, including substituents, is 50 or less, more preferably 40 or less, and particularly preferably 30 or less. When the total number of carbon atoms is 50 or less, the synthesis of compound (I) (dye) becomes easier, and the absorption intensity per unit mass can be improved.

[0022] <<Condition (ii)>> In formula (I), at least one R bonded to one benzene ringa And, R a The adjacent Y atoms bond to each other to form a heterocycle with 5 or 6 members containing at least one nitrogen atom, and the heterocycle may have substituents. R b and R that does not participate in the formation of the heterocycle a Each of these independently corresponds to R of condition (i) above. b and R a It is synonymous with [the above].

[0023] Said L a Examples of aliphatic hydrocarbon groups having 1 to 9 carbon atoms in L include alkyl groups such as methyl (Me), ethyl (Et), n-propyl (n-Pr), isopropyl (i-Pr), n-butyl (n-Bu), sec-butyl (s-Bu), tert-butyl (t-Bu), pentyl, hexyl, octyl, and nonyl groups; alkenyl groups such as vinyl, 1-propenyl, 2-propenyl, butenyl, 1,3-butadienyl, 2-methyl-1-propenyl, 2-pentenyl, hexenyl, and octenyl groups; and alkynyl groups such as ethynyl, propynyl, butynyl, 2-methyl-1-propynyl, hexynyl, and octinyl groups.

[0024] Said L b Examples of halogen-substituted alkyl groups having 1 to 9 carbon atoms in L include trichloromethyl, trifluoromethyl, 1,1-dichloroethyl, pentachloroethyl, pentafluoroethyl, heptachloropropyl, and heptafluoropropyl groups.

[0025] Said L c Examples of alicyclic hydrocarbon groups having 3 to 14 carbon atoms in L include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, norbornane, and cycloalkyl groups such as adamantane.

[0026] Said L dExamples of aromatic hydrocarbon groups having 6 to 14 carbon atoms in L include phenyl, tolyl, xylyl, mesityl, cumenyl, 1-naphthyl, 2-naphthyl, anthracenyl, phenanthryl, acenaphthyl, phenalenyl, tetrahydronaphthyl, indanyl, and biphenylyl groups.

[0027] Said L e Examples of heterocyclic groups having 3 to 14 carbon atoms in L include furan, thiophene, pyrrole, pyrazole, imidazole, triazole, oxazole, oxadiazole, thiazole, thiadiazole, indole, indoline, indorenine, benzofuran, benzothiophene, carbazole, dibenzofuran, dibenzothiophene, pyridine, pyrimidine, pyrazine, pyridazine, quinoline, isoquinoline, acridine, and phenazine.

[0028] Said L f Examples of alkoxy groups having 1 to 9 carbon atoms in this context include methoxy, ethoxy, propoxy, isopropoxy, butoxy, 2-methoxyethoxy, pentyloxy, hexyloxy, octyloxy, methoxymethyl, methoxyethyl, methoxypropyl, methoxybutyl, methoxyhexyl, ethoxyethyl, ethoxyethyl, ethoxypropyl, ethoxybutyl, ethoxyhexyl, propoxymethyl, propoxypropyl, propoxyhexyl, and butoxyethyl groups.

[0029] Said L g Examples of acyl groups having 1 to 9 carbon atoms in this context include acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, and benzoyl groups.

[0030] Said L hExamples of alkoxycarbonyl groups having 1 to 9 carbon atoms include methoxycarbonyl group, ethoxycarbonyl group, propoxycarbonyl group, isopropoxycarbonyl group, butoxycarbonyl group, 2-methoxyethoxycarbonyl group, pentyloxycarbonyl group, hexyloxycarbonyl group, and octyloxycarbonyl group.

[0031] Said L a Examples include the "aliphatic hydrocarbon group having 1 to 9 carbon atoms" mentioned above, and the aliphatic hydrocarbon group further having the substituent L. Among these, L a Preferably, the group is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group, octyl group, 4-phenylbutyl group, or 2-cyclohexylethyl group, and more preferably a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, sec-butyl group, or tert-butyl group.

[0032] Said L b Examples include the above-mentioned "halogen-substituted alkyl groups having 1 to 9 carbon atoms," and the halogen-substituted alkyl groups further having the substituent L. Among these, L b Preferably, the group is a trichloromethyl group, a pentachloroethyl group, a trifluoromethyl group, a pentafluoroethyl group, a 5-cyclohexyl-2,2,3,3-tetrafluoropentyl group, or a 2,2-dichloro-4-phenoxybutyl group, and more preferably a trichloromethyl group, a pentachloroethyl group, a trifluoromethyl group, or a pentafluoroethyl group.

[0033] Said L c Examples include the "alicyclic hydrocarbon group having 3 to 14 carbon atoms" mentioned above, and the alicyclic hydrocarbon group further having the substituent L. Among these, L cPreferably, the group is a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a 4-ethylcyclohexyl group, a cyclooctyl group, or a 4-phenylcycloheptyl group, and more preferably a cyclopentyl group, a cyclohexyl group, or a 4-ethylcyclohexyl group.

[0034] Said L d Examples include the "aromatic hydrocarbon group having 6 to 14 carbon atoms" mentioned above, and the aromatic hydrocarbon group further having the substituent L. Among these, L d Preferably, the group is a phenyl group, a 1-naphthyl group, a 2-naphthyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 3,5-di-tert-butylphenyl group, a 4-cyclopentylphenyl group, a 2,3,6-triphenylphenyl group, a 2,3,4,5,6-pentaphenylphenyl group, or a 4-α-cumylphenoxy group, and more preferably a phenyl group, a tolyl group, a xylyl group, a mesityl group, a cumenyl group, a 2,3,4,5,6-pentaphenylphenyl group, or a 4-α-cumylphenoxy group.

[0035] Said L e Examples include the "heterocyclic group having 3 to 14 carbon atoms" mentioned above, and the heterocyclic group further having the substituent L. Among these, L e Preferably, the group is composed of furan, thiophene, pyrrole, indole, indoline, indorenine, benzofuran, or benzothiophene, and more preferably, furan, thiophene, or pyrrole.

[0036] Said L f Examples include the "alkoxy group having 1 to 9 carbon atoms" mentioned above, and the alkoxy group further having the substituent L. Among these, L fPreferably, the group is a methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, 2-methoxyethoxy group, methoxymethyl group, methoxyethyl group, 2-phenylethoxy group, 3-cyclohexylpropoxy group, pentyloxy group, hexyloxy group, or octyloxy group, and more preferably a methoxy group, ethoxy group, propoxy group, isopropoxy group, or butoxy group.

[0037] Said L g Examples include the "acyl group having 1 to 9 carbon atoms" mentioned above, and the acyl group further having the substituent L. Among these, L g The preferred group is an acetyl group, a propionyl group, a butyryl group, an isobutyryl group, a benzoyl group, or a 4-propylbenzoyl group, and more preferably an acetyl group, a propionyl group, or a benzoyl group.

[0038] Said L h Examples include the "alkoxycarbonyl group having 1 to 9 carbon atoms" mentioned above, and the alkoxycarbonyl group further having the substituent L. Among these, L h Preferably, the group is a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a 2-trifluoromethylethoxycarbonyl group, or a 2-phenylethoxycarbonyl group, and more preferably a methoxycarbonyl group or an ethoxycarbonyl group.

[0039] Said L a ~L h It may further have at least one atom or group selected from the group consisting of halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and amino groups. Examples of such groups include 4-sulfobutyl group, 4-cyanobutyl group, 5-carboxypentyl group, 5-aminopentyl group, 3-hydroxypropyl group, 2-phosphorylethyl group, 6-amino-2,2-dichlorohexyl group, 2-chloro-4-hydroxybutyl group, 2-cyanocyclobutyl group, 3-hydroxycyclopentyl group, 3-carboxycyclopentyl group, 4-aminocyclohexyl group, 4-hydroxycyclohexyl group, 4-hydroxyphenyl group, pentafluorophenyl group, 2-hydroxynaphthyl group, 4-aminophenyl group, 2,3,4,5,6-pentafluorophenyl group, 4-nitrophenyl group, a group consisting of 3-methylpyrrole, 2-hydroxyethoxy group, 3-cyanopropoxy group, 4-fluorobenzoyl group, 2-hydroxyethoxycarbonyl group, and 4-cyanobutoxycarbonyl group.

[0040] R in the above condition (i) a Preferably, the group is a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a hydroxyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, an amino group, a dimethylamino group, or a nitro group, and more preferably, a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, or a hydroxyl group.

[0041] The aforementioned R bPreferably, the group is a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a tert-butyl group, a cyclohexyl group, a phenyl group, an amino group, a dimethylamino group, a cyano group, a nitro group, a hydroxyl group, an acetylamino group, a propionylamino group, an N-methylacetylamino group, a trifluoromethylamino group, a pentafluoroethanolamino group, a t-butanoylamino group, or a cyclohexinoylamino group. More preferably, the group is a hydrogen atom, a chlorine atom, a fluorine atom, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a dimethylamino group, a nitro group, a hydroxyl group, an acetylamino group, a propionylamino group, a trifluoromethylamino group, a pentafluoroethanolamino group, a t-butanoylamino group, or a cyclohexinoylamino group.

[0042] The aforementioned Y is preferably an amino group, a methylamino group, a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, a di-t-butylamino group, an N-ethyl-N-methylamino group, or an N-cyclohexyl-N-methylamino group, and more preferably a dimethylamino group, a diethylamino group, a di-n-propylamino group, a diisopropylamino group, a di-n-butylamino group, or a di-t-butylamino group.

[0043] In condition (ii) of formula (I), at least one R bonded to one benzene ring a And, R a Examples of heterocycles with 5 or 6 members containing at least one nitrogen atom, formed by the mutual bonding of adjacent Y and other atoms, include pyrrolidine rings, pyrrole rings, imidazole rings, pyrazole rings, piperidine rings, pyridine rings, piperazine rings, pyridazine rings, pyrimidine rings, and pyrazine rings. Among these heterocycles with 5 or 6 members, a heterocycle constituting the heterocycle and in which one atom adjacent to the carbon atom constituting the benzene ring is a nitrogen atom is preferred, and a pyrrolidine ring is even more preferred.

[0044] Compound (I) can be represented structurally in the manner shown in formula (I-1) below, as well as in the manner shown in formula (I-2) below, which involves a resonance structure. In other words, the only difference between formula (I-1) and formula (I-2) below is the method of structural description; both represent the same compound. In this invention, unless otherwise specified, the structure of squarylium compounds will be represented in the manner shown in formula (I-1) below.

[0045] [ka]

[0046] [ka]

[0047] The structure of compound (I) is not particularly limited as long as it satisfies either condition (i) or (ii) of formula (I) above. For compound (I), for example, when represented by the structure of formula (I-1) above, the substituents on the left and right sides attached to the central four-membered ring may be the same or different, but from the viewpoint of ease of synthesis, it is preferable that the substituents on the left and right sides attached to the central four-membered ring are the same. For example, the compound represented by the following formula (I-3) and the compound represented by the following formula (I-4) can be considered to be the same compound.

[0048] [ka]

[0049] Specific examples of compound (I) include the exemplary compounds (a-1) to (a-31) listed in Tables 1 to 3 below, which have the basic skeleton represented by (IA) to (IF) below; however, compound (I) in the present invention is not limited to these compounds.

[0050] [ka] [ka]

[0051] [Table 1]

[0052] [Table 2]

[0053] [Table 3]

[0054] Compound (I) can be synthesized by generally known methods, for example, by referring to the methods described in Japanese Patent Publication No. 1-228960, Japanese Patent Publication No. 2001-40234, Japanese Patent No. 3196383, etc.

[0055] The absorption maximum wavelength of compound (I) is preferably 600 to 800 nm, more preferably 620 to 760 nm, and particularly preferably 650 to 740 nm. When the absorption maximum wavelength is within this wavelength range, it is possible to achieve both sufficient near-infrared absorption characteristics and visible light transmittance.

[0056] In the above method for producing the film, compound (I) may be used alone or in combination of two or more types.

[0057] <<Vacuum Deposition Method>> In the film manufacturing method according to the present invention, a known vacuum deposition method can be used. Examples of vacuum deposition methods include resistance heating deposition and electron beam heating deposition. Vacuum deposition allows for the adjustment of desired film properties by appropriately setting the heating method of compound (I) used in the vacuum deposition method, the shape of the deposition source such as the crucible and boat, the degree of vacuum, the temperature of the deposition source, the substrate temperature, the deposition rate, and so on. There are no particular restrictions on the method of depositing compound (I) onto the substrate; from the viewpoint of uniformly depositing compound (I) onto the substrate, the substrate may be rotated while depositing compound (I).

[0058] In vacuum deposition, a higher vacuum level is preferable, and more preferably 10 -4 Torr(≒10 -2 Pa) or less, more preferably 10 -6 Torr(≒10 -4 Pa) or less, particularly preferably 10 -8 Torr(≒10 -6 Pa) is less than or equal to [amount]. Furthermore, the vacuum deposition process is preferably carried out in a vacuum, and it is preferable to perform the vacuum deposition in an environment where compound (I) does not come into direct contact with oxygen and moisture in the outside air.

[0059] Examples of source temperatures include 150-200°C. Examples of substrate temperatures include -20 to 100°C. Examples of deposition rates include 0.05 nm / min to 1.00 nm / min.

[0060] Since the above-mentioned conditions for vacuum deposition affect the crystallinity, amorphousness, density, and density of the organic film, it is preferable that the deposition rate is controlled by PI or PID using a film thickness monitor such as a quartz crystal oscillator or interferometer during the vacuum deposition process. When two or more compounds (I) are deposited simultaneously, vacuum deposition methods such as co-deposition and flash deposition can be suitably used.

[0061] An example of a vacuum deposition process is the film formation method described in the examples below, but the present invention is not limited thereto.

[0062] There are no particular restrictions on the substrate used in the vacuum deposition process, and examples include glass plates, steel belts, steel drums, and transparent resins (e.g., polyester film, cyclic olefin resin film).

[0063] [Other processes] The film manufacturing method may include steps other than the vacuum deposition process (other steps) as needed. Examples of other steps include a step of preparing compound (I), a step of purifying the compound, a step of adjusting the particle size, a step of cleaning the substrate, and a step of surface treatment of the substrate.

[0064] Furthermore, in the method for manufacturing the film, compound (I) and compounds other than compound (I) (hereinafter also referred to as "other compounds") may be deposited by vacuum deposition. Examples of other compounds include squarylium-based compounds other than compound (I) and phthalocyanine compounds.

[0065] The film thickness is preferably 5 to 1000 nm, more preferably 10 to 500 nm, and even more preferably 20 to 200 nm, from the viewpoint of having excellent optical properties such as shielding against near-infrared light.

[0066] <Optical filters> From the viewpoint of being able to produce a thin film with excellent optical properties and in-plane uniformity, and having a small difference between the wavelength at which absorbance is minimum in the visible light region and the wavelength at which absorbance is maximum in the near-infrared region, it is preferable that the film obtained by the film manufacturing method according to the present invention be an optical filter.

[0067] The optical filter obtained by the film manufacturing method according to the present invention may have a resin substrate containing a resin and a near-infrared absorbing dye containing the above compound (I). The optical filter may also have a near-infrared reflective film. A transparent resin is preferred as the resin mentioned above. Such a resin is not particularly limited as long as it does not impair the effects of the present invention, but for example, a resin having a glass transition temperature (Tg) of preferably 110 to 380°C, more preferably 110 to 370°C, and even more preferably 120 to 360°C is recommended in order to ensure thermal stability and moldability into a film, and to obtain a film that can form a dielectric multilayer film by high-temperature deposition performed at a deposition source temperature of 100°C or higher. Furthermore, a glass transition temperature of 140°C or higher is particularly preferred because it allows for the deposition and formation of a dielectric multilayer film at an even higher temperature.

[0068] Furthermore, the resin used is one in which the total light transmittance (JIS K7105) at a thickness of 0.1 mm is preferably 75 to 95%, more preferably 78 to 95%, and particularly preferably 80 to 95%. If the total light transmittance is within this range, the resulting substrate will exhibit good transparency as an optical filter.

[0069] Examples of the aforementioned resins include cyclic polyolefin resins, aromatic polyether resins, polyimide resins, fluorene polycarbonate resins, fluorene polyester resins, polycarbonate resins, polyamide (aramid) resins, polyarylate resins, polysulfone resins, polyethersulfone resins, poly-paraphenylene resins, polyamide-imide resins, polyethylene naphthalate (PEN) resins, fluorinated aromatic polymer resins, (modified) acrylic resins, epoxy resins, allyl ester-based curable resins, and silsesquioxane-based UV-curable resins.

[0070] The transparent resins mentioned above may be commercially available products. Examples of commercially available cyclic olefin resins include Arton manufactured by JSR Corporation, Zeon Corporation's Zeonor, Mitsui Chemicals, Inc.'s APEL, and Polyplastics Corporation's TOPAS. Examples of commercially available polyethersulfone resins include Sumika Excel PES manufactured by Sumitomo Chemical Co., Ltd. Examples of commercially available polyimide resins include Neoprim L manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available polycarbonate resins include Pureace manufactured by Teijin Limited. Examples of commercially available fluorene polycarbonate resins include Yupizeta EP-5000 manufactured by Mitsubishi Gas Chemical Company, Inc. Examples of commercially available fluorene polyester resins include OKP4HT manufactured by Osaka Gas Chemical Co., Ltd. Examples of commercially available acrylic resins include Acryvia manufactured by Nippon Shokubai Co., Ltd. Examples of commercially available silsesquioxane UV curing resins include Silplus manufactured by Nippon Steel Chemical Co., Ltd.

[0071] [Resin substrate] The resin substrate may be single-layer or multi-layer, and preferably contains the above compound (I) as a near-infrared absorbing dye, with an absorption maximum in the wavelength range of 600 to 800 nm. If the absorption maximum wavelength of the substrate is in this range, the substrate can selectively and efficiently cut near-infrared rays.

[0072] When such a resin substrate is used in an optical filter such as a near-infrared cut filter, the absolute value of the difference between the wavelength value (Xa) at which the transmittance is 50% when measured perpendicular to the optical filter and the wavelength value (Xb) at which the transmittance is 50% when measured at an angle of 30° to the perpendicular to the optical filter becomes small in the wavelength range of 560 to 800 nm. This results in an optical filter with a small incident angle dependence of the absorption wavelength and a wide field of view. The absolute value of the difference between (Xa) and (Xb) is preferably less than 20 nm, more preferably less than 15 nm, and particularly preferably less than 10 nm.

[0073] Depending on the application, such as a camera module, it is preferable that the average transmittance of a resin substrate containing the above compound (I) is 50% or more, preferably 65% ​​or more, in the so-called visible light region of 400 to 700 nm wavelength, when the thickness of the substrate is 100 μm.

[0074] The thickness of the resin substrate can be appropriately selected according to the desired application and is not particularly limited, but it is preferable to adjust the substrate so that it has the incidence angle dependence described above, more preferably 30 to 250 μm, even more preferably 40 to 200 μm, and particularly preferably 50 to 150 μm.

[0075] When the thickness of the resin substrate is within the aforementioned range, the optical filter using the substrate can be made smaller and lighter, making it suitable for various applications such as solid-state imaging devices. In particular, when the resin substrate is used in a lens unit such as a camera module, it is preferable because it enables a reduction in the height of the lens unit.

[0076] In addition to compound (I), the resin substrate may contain, as a near-infrared absorbing dye, squarylium-based compounds and phthalocyanine-based compounds other than compound (I), and at least one near-ultraviolet absorber selected from the group consisting of azomethine-based compounds, indole-based compounds, benzotriazole-based compounds, and triazine-based compounds. By using such a resin substrate, an optical filter with low incident angle dependence and a wide viewing angle can be obtained even in the near-ultraviolet wavelength region.

[0077] The near-infrared absorbing dye and the near-ultraviolet absorbing agent may be contained in the same layer or in separate layers. When contained in the same layer, for example, the near-infrared absorbing dye and the near-ultraviolet absorbing agent may both be contained in the same resin substrate. When contained in separate layers, for example, a layer containing the near-ultraviolet absorbing agent may be laminated on a resin substrate containing the near-infrared absorbing dye. It is more preferable that the near-ultraviolet absorber and the near-infrared absorbing dye are contained in the same layer. In this case, it becomes easier to control the content ratio of the near-infrared absorbing dye and the near-ultraviolet absorber compared to when they are contained in separate layers.

[0078] [Characteristics of optical filters, etc.] The optical filter has a substrate on which the compound (I) is deposited by vacuum deposition. Therefore, the optical filter of the present invention is a thin film in which the difference between the wavelength at which absorbance is minimum in the visible light region and the wavelength at which absorbance is maximum in the near-infrared region is small, and an optical filter with high transmittance contrast between the visible light transmission region and the near-infrared absorption region can be obtained.

[0079] [Applications of optical filters] The optical filters obtained by the film manufacturing method according to the present invention have a wide viewing angle and excellent near-infrared cut capability. Therefore, they are useful for correcting the luminous sensitivity of solid-state image sensors such as CCD and CMOS image sensors in camera modules. In particular, they are useful in digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automotive cameras, televisions, car navigation systems, personal information terminals, personal computers, video games, portable game consoles, fingerprint authentication systems, digital music players, etc. Furthermore, they are also useful as heat-cut filters attached to glass in automobiles, buildings, etc. [Examples]

[0080] The present invention will be described in more detail below based on examples, but the present invention is not limited in any way to these examples. Unless otherwise specified, "parts" refers to "parts by mass." The methods for measuring each physical property and evaluating the physical properties are as follows.

[0081] <Spectral transmittance> The absorption maximum wavelength (λa), the minimum absorbance wavelength in the visible light range (λb), and the transmittance of the film-coated substrate (optical filter) fabricated as described later were measured using a spectrophotometer (Hitachi High-Technologies Corporation, model number: U-4100). Here, the transmittance measured from the perpendicular direction of the optical filter was determined by measuring the light transmitted perpendicularly to the filter, as shown in Figure 1.

[0082] <Absorption maximum wavelength (λa) - Absorbance minimum wavelength in the visible light region (λb)> The difference between the wavelength at which absorbance is minimum in the visible light region and the wavelength at which absorbance is maximum in the near-infrared region was determined as the absolute value (|λa-λb|) obtained by subtracting the wavelength at which absorbance is minimum in the visible light region (λb) from the wavelength at which absorption is maximum (λa) of the obtained optical filter. When |λa-λb| is 260 or less, the difference between the wavelength at which absorbance is minimum in the visible light region and the wavelength at which absorbance is maximum in the near-infrared region is small, indicating that an optical filter with high contrast has been obtained.

[0083] <In-plane uniformity> Using a UV-Vis spectrophotometer (manufactured by JASCO Corporation, model number: V-7200) and an absolute reflectance measurement unit (manufactured by JASCO Corporation, model number: VAR-7030), transmittance was measured at a total of five points (four vertices and one center) of a 1cm square optical filter within a 1mmφ range, in accordance with CIE 1976 L in accordance with section 4.1 of JIS Z8781-4. * a * b * These were calculated separately. The tristimulus values ​​Xn, Yn, and Zn of the test color stimuli in the CIE 1931 color system used in the calculation were X10, Y10, and Z10 as defined in JIS Z 8781-1. (5 locations L) * a * b * The ΔL for each combination from the value * Δa * Δb * Find ΔE * ab=[(ΔL * ) 2 +(Δa * )2 +(Δb * ) 2 ] 1 / 2 From the color difference (ΔE * Calculate ab) and find the maximum color difference (ΔE * a max ) was sought. The in-plane uniformity of the obtained color difference was evaluated according to the following criteria: Color difference (ΔE * When the ab max is 10 or less, optical variations are suppressed, and the in-plane uniformity is excellent. -Evaluation Criteria- 〇:ΔE * a max ≤ 10 ×:ΔE * a max > 10

[0084] <Optical properties> The optical properties of the obtained optical filter were evaluated according to the following criteria based on its transmittance at the absorption maximum wavelength (λa). A transmittance of 50% or less at the absorption maximum wavelength (λa) indicates excellent shielding of near-infrared light and superior optical properties in the near-infrared region. -Evaluation Criteria- ○: Transmittance at the absorption maximum wavelength (λa) ≤ 50% ×: Transmittance > 50% at the absorption maximum wavelength (λa)

[0085] [Example 1] Vacuum deposition was performed using the dyes listed in Table 4, following the procedure below. First, the cleaned substrate (glass slide: manufactured by Matsunami Glass Industry Co., Ltd., model number: S1111) is fixed to the substrate stage inside the chamber, then 3.0 × 10 -4 Vacuum evacuation was performed until the pressure fell below Pa. The substrate temperature was controlled to a constant temperature by a heater attached to the substrate stage and by cooling through the circulation of coolant (liquid nitrogen in this case) inside the substrate stage. Furthermore, an alumina crucible containing the raw material (dye), which serves as the deposition source, was placed in a basket made of tungsten filament, and the tungsten filament was heated by applying an electric current to bring the deposition sample to the deposition source temperature shown in Table 4. While monitoring the deposition rate using a quartz crystal thickness gauge attached to the side of the substrate stage, the current value was adjusted using a variac to achieve a deposition rate of 0.2-0.3 nm / min. The substrate temperature was controlled to the temperatures listed in Table 4, and after confirming that the target deposition rate had been reached, the shutter was opened to begin film deposition on the substrate. The film thickness was measured using a quartz crystal film thickness gauge, and a film was deposited to a thickness of 30 nm to create a substrate (optical filter) with the film attached. Using the spectrophotometer described above, the absorption maximum wavelength (λa), transmittance at the absorption maximum wavelength (λa), and minimum absorbance wavelength (λb) of the obtained substrate were measured, and the in-plane uniformity and optical properties were evaluated. The results are shown in Table 4.

[0086] [Examples 2-10 and Comparative Examples 4-6] Vacuum deposition was performed under the conditions shown in Table 4, in the same manner as in Example 1, except that the dyes listed in Table 4 were used, and a film was deposited to the thickness shown in Table 4 to create a film-coated substrate (optical filter). In the same manner as in Example 1, the absorption maximum wavelength (λa), transmittance at the absorption maximum wavelength (λa), and minimum absorbance wavelength (λb) of the obtained substrate were measured using a spectrophotometer, and the in-plane uniformity and optical properties were evaluated. The results are shown in Table 4.

[0087] [Comparative Example 1] Using the dyes listed in Table 4, spin coating 1 (dye in a single solvent) was performed as follows. The dye (Compound 1) shown in Table 4 was dissolved in ethanol at a concentration of 0.04% by mass, and a film was deposited on a substrate (glass slide (Matsunami Glass Industry Co., Ltd., model number: S1111)) by spin coating to fabricate a film-coated substrate (optical filter). The spin coating rotation speed was 800 rpm and the rotation time was 10 seconds. In the same manner as in Example 1, the absorption maximum wavelength (λa), transmittance at the absorption maximum wavelength (λa), and minimum absorbance wavelength (λb) of the film-coated substrate obtained were measured using a spectrophotometer, and the in-plane uniformity and optical properties were evaluated. The results are shown in Table 4.

[0088] [Comparative Example 2] Using the dyes listed in Table 4, spin coating 1 (dye in a single solvent) was performed as follows. The dye (Compound 1) shown in Table 4 was dissolved in dichloromethane at a concentration of 1% by mass, and a film was deposited on a substrate (glass slide (Matsunami Glass Industry Co., Ltd., S1111)) by spin coating to fabricate a film-coated substrate (optical filter). The spin coating speed was 500 rpm and the spin time was 30 seconds. In the same manner as in Example 1, the absorption maximum wavelength (λa), transmittance at the absorption maximum wavelength (λa), and minimum absorbance wavelength (λb) of the film-coated substrate obtained were measured using a spectrophotometer, and the in-plane uniformity and optical properties were evaluated. The results are shown in Table 4.

[0089] [Comparative Example 3] Spin coating 2 (dye-containing resin solution) was performed using the dye (compound 1) listed in Table 4 as follows. In a container, 2 parts by mass of novolac resin (product name "Sumilite Resin PR-12603") manufactured by Sumitomo Bakelite Co., Ltd., 98 parts by mass of cyclic olefin resin (manufactured by JSR Corporation, product name "ARTON R5000"), and 0.45 parts by mass of compound 1 and toluene were added to a total of 100 parts by mass of these resins to obtain a solution (ex1) with a resin concentration of 25% by mass. Next, the obtained solution was deposited onto a glass slide (Matsunami Glass Industry Co., Ltd., model number: S1111) by spin coating. The rotation speed was 300 rpm and the rotation time was 10 seconds. The coated glass slide was dried on a hot plate at 100°C for 180 seconds, and then heat-treated in an oven at 160°C for 20 minutes under atmospheric conditions. At this time, the film thickness was controlled so that the optical properties were ○ (i.e., the transmittance at the absorption maximum wavelength (λa) was 50% or less), and a film-coated substrate (optical filter) was fabricated. In the same manner as in Example 1, the absorption maximum wavelength (λa), transmittance at the absorption maximum wavelength (λa), and minimum absorbance wavelength (λb) of the obtained film-coated substrate were measured using a spectrophotometer, and the in-plane uniformity and optical properties were evaluated. However, no matter how the concentration of the dye in the dye-containing resin solution was adjusted, it was not possible to deposit a film with a thickness of 3 μm or less. The results are shown in Table 4.

[0090] [Table 4]

[0091] The details of the pigments in Table 4 are as follows: Compound 1: Compound (a-21) listed in Table 2 • Comparative compound 1: Compound represented by the following structure

[0092] [ka]

[0093] • Comparative compound 2: Compound represented by the following structure

[0094] [ka]

[0095] Comparative compound 3: Compound represented by the following structure

[0096] [ka] [Industrial applicability]

[0097] Optical filters obtained by the film manufacturing method according to the present invention can be suitably used in digital still cameras, mobile phone cameras, digital video cameras, PC cameras, surveillance cameras, automobile cameras, televisions, car navigation systems, personal information terminals, personal computers, video games, portable game consoles, fingerprint authentication systems, digital music players, and the like. The above optical filters can also be suitably used as heat-cutting filters attached to glass in automobiles, buildings, etc. [Explanation of symbols]

[0098] 8: Optical filters 9: Spectrophotometer

Claims

1. A method for producing a film, comprising forming a film of a compound represented by the following general formula (I) by vacuum deposition. 【Chemistry 1】 [In formula (I), R ａ , R ｂ And Y satisfies either condition (i) or (ii) below. (i) A plurality of Rs ａ are each independently a hydrogen atom, a halogen atom, a sulfo group, a hydroxyl group, a cyano group, a nitro group, a carboxy group, a phosphoric acid group, -L １ or -NR ｅ R ｆ group (where the said R ｅ and R ｆ each independently represent a hydrogen atom, -L ａ , -L ｂ , -L ｃ , -L ｄ or -L ｅ ).) represents, Multiple R ｂ These are independently hydrogen atoms, halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and -L １ or -NR ｇ R ｈ Base (the R ｇ and R ｈ Each is an independent hydrogen atom, -L ａ , -L ｂ , -L ｃ , -L ｄ , -L ｅ or -C(O)R ｉ Base (the R ｉ is, -L ａ , -L ｂ , -L ｃ , -L ｄ or -L ｅ It represents. ) It represents. ) It represents, The multiple Ys are independently -NR ｊ R ｋ Base (the R ｊ and R ｋ Each is an independent hydrogen atom, -L ａ、 -L ｂ , -L ｃ , -L ｄ or -L ｅ It represents. Said L １ teeth, (L ａ ) A C1-C9 aliphatic hydrocarbon group which may have a substituent L, (L ｂ ) A halogen-substituted alkyl group of 1 to 9 carbon atoms which may have substituent L, (L ｃ ) A cycloaliphatic hydrocarbon group having 3 to 14 carbon atoms, which may have substituent L. (L ｄ ) A C6 to C14 aromatic hydrocarbon group which may have substituent L, (L ｅ ) A heterocyclic group having 3 to 14 carbon atoms, which may have substituent L. (L ｆ ) A carbon-1 to carbon-9 alkoxy group which may have a substituent L, (L ｇ ) A carbon-1 to carbon-9 acyl group which may have a substituent L, or (L ｈ ) A C1-C9 alkoxycarbonyl group which may have a substituent L The substituent L is at least one group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a halogen-substituted alkyl group having 1 to 9 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms. ａ ~L ｈ It may further have at least one atom or group selected from the group consisting of halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and amino groups. (ii) at least one R bonded to one benzene ring ａ And, R ａ The adjacent Y atoms bond to each other to form a heterocycle with 5 or 6 members containing at least one nitrogen atom, and the heterocycle may have substituents. R ｂ and R that does not participate in the formation of the heterocycle ａ Each of these independently corresponds to R of condition (i) above. ｂ and R ａ This is synonymous with [the above].

2. The method for producing a film according to claim 1, wherein the resulting film is an optical filter.

3. A compound used for film formation by vacuum deposition, represented by the following general formula (I). 【Chemistry 2】 [In formula (I), R ａ , R ｂ And Y satisfies either condition (i) or (ii) below. (i) Multiple R ａ These are independently hydrogen atoms, halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and -L １ or -NR ｅ R ｆ Base (the R ｅ and R ｆ These are, independently, hydrogen atoms and -L ａ , -L ｂ , -L ｃ , -L ｄ or -L ｅ It represents. Multiple R ｂ These are independently hydrogen atoms, halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and -L １ or -NR ｇ R ｈ Base (the R ｇ and R ｈ Each is an independent hydrogen atom, -L ａ , -L ｂ , -L ｃ , -L ｄ , -L ｅ or -C(O)R ｉ Base (the R ｉ is, -L ａ , -L ｂ , -L ｃ , -L ｄ or -L ｅ It represents. ) It represents. ) It represents, A plurality of Ys are independently -NR ｊ R ｋ group (where said R ｊ and R ｋ each independently represents a hydrogen atom, -L ａ , -L ｂ , -L ｃ , -L ｄ or -L ｅ ).). Said L １ teeth, (L ａ ) A C1-C9 aliphatic hydrocarbon group which may have a substituent L, (L ｂ ) A halogen-substituted alkyl group of 1 to 9 carbon atoms which may have substituent L, (L ｃ ) A cycloaliphatic hydrocarbon group having 3 to 14 carbon atoms, which may have substituent L. (L ｄ ) A C6 to C14 aromatic hydrocarbon group which may have substituent L, (L ｅ ) A heterocyclic group having 3 to 14 carbon atoms, which may have substituent L. (L ｆ ) A carbon-1 to carbon-9 alkoxy group which may have a substituent L, (L ｇ ) A carbon-1 to carbon-9 acyl group which may have a substituent L, or (L ｈ ) A C1-C9 alkoxycarbonyl group which may have a substituent L The substituent L is at least one group selected from the group consisting of an aliphatic hydrocarbon group having 1 to 9 carbon atoms, a halogen-substituted alkyl group having 1 to 9 carbon atoms, an alicyclic hydrocarbon group having 3 to 14 carbon atoms, an aromatic hydrocarbon group having 6 to 14 carbon atoms, and a heterocyclic group having 3 to 14 carbon atoms. ａ ~L ｈ It may further have at least one atom or group selected from the group consisting of halogen atoms, sulfo groups, hydroxyl groups, cyano groups, nitro groups, carboxyl groups, phosphoric acid groups, and amino groups. (ii) at least one R bonded to one benzene ring ａ And, the aforementioned R ａ The adjacent Y and the other are bonded to each other to form a heterocycle with 5 or 6 members containing at least one nitrogen atom, and the heterocycle may have substituents. R ｂ and R that does not participate in the formation of the heterocycle ａ Each of these independently corresponds to R of condition (i) above. ｂ and R ａ This is synonymous with [the above].

Images