Compound, its tautomer or salt thereof, production method thereof, coloring composition, dyeing method, and dyed product

Abstract

The present invention provides: a compound represented by formula 1, a tautomer of the compound, and a salt of the compound or tautomer; a method for producing the compound, tautomer or salt; a coloring composition and a dyed article, each of which contains a compound represented by formula 1, a tautomer of the compound, or a salt of the compound or tautomer; and a dyeing method which uses a compound represented by formula 1, a tautomer of the compound, or a salt of the compound or tautomer. In formula 1, X, R, Ar, n and m1 are as defined in the description.

Description

[Technical Field]

[0001] The present disclosure relates to a compound, a tautomer thereof, or a salt thereof, a method for producing the same, a coloring composition, a dyeing method, and a dyed product. [Background technology]

[0002] Conventionally, azo dyes have been used as dyes in various fields, since they often have various visible light absorption properties, such as coloring synthetic resins, printing inks, dyes for dye-sublimation thermal transfer materials, inkjet inks, and dyes for color filters.

[0003] In recent years, color images have become mainstream as image recording materials, and the applications of dyes have become more diverse. Specifically, dyes are widely used in inkjet recording materials, thermal transfer recording materials, electrophotographic recording materials, transfer-type silver halide photosensitive materials, printing inks, and the like. Furthermore, color filters for recording and reproducing color images are used in imaging devices such as solid-state image sensors (CCDs) and complementary metal-oxide semiconductors (CMOSs) in photographic equipment, and in liquid crystal displays (LCDs) and plasma display panels (PDPs) in displays. These color image recording materials and color filters use colorants (dyes or pigments) of the three primary colors of the additive or subtractive color mixing method to reproduce or record full-color images.

[0004] Furthermore, various dyes for dyeing fibers and the like have been known for a long time, and in recent years, many hair dyes for dyeing hair and the like have been developed. Hair dyes can be classified according to the dye used or whether they have a bleaching effect on melanin. Representative examples of hair dyes include two-component permanent hair dyes consisting of a first component containing an alkaline agent, an oxidation dye, and optionally a direct dye such as a nitro dye, and a second component containing an oxidizing agent, and one-component semi-permanent hair dyes containing an organic acid or alkaline agent and at least one direct dye such as an acid dye, a basic dye, or a nitro dye.

[0005] Examples of conventional azo dyes include those described in JP-A-2017-515930. Summary of the Invention [Problem to be solved by the invention]

[0006] However, there are cases where dyes with special hues other than the conventional yellow, magenta, and cyan are required. For example, dyes with low saturation or dyes with a wide absorption waveform that absorbs light across the entire visible range are required. Therefore, there are currently no colorants that have these desirable absorption characteristics and are robust enough to withstand various usage and environmental conditions, and improvements are strongly desired.

[0007] The problem that embodiments of the present invention aim to solve is to provide novel compounds, their tautomers, or salts thereof. Another problem to be solved by the present invention is to provide a coloring composition that has a low chroma hue. A problem to be solved by still another embodiment of the present invention is to provide a method for producing the above-mentioned compound, a tautomer thereof, or a salt thereof, as well as a dyeing method and a dyed product dyed with the above-mentioned compound, a tautomer thereof, or a salt thereof. [Means for solving the problem]

[0008] The means for solving the above problems include the following aspects. <1> A compound represented by the following formula 1, a tautomer thereof, or a salt thereof.

[0009] [ka]

[0010] In Formula 1, X- represents R 1 O-, R 2a R 2b N- or R 3 S- represents R 1 , R 2a and R 2beach independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group. X- is R 2a R 2b If N-, R 2a and R 2b may be the same or different, and R 2a and R 2b may bond to form a nitrogen-containing heterocycle. Each R independently represents a substituent, n represents 0, 1, 2, or 3, and when n represents 2 or 3, the Rs may be the same or different. Ar represents an aromatic hydrocarbon group or a heterocyclic group, m1 represents 1, 2, or 3, and when m1 represents 2 or 3, the Ars may be the same or different, provided that at least one Ar is a heterocyclic group.

[0011] <2> m1 is 2 or 3 <1> 1. The compound according to claim 1, a tautomer thereof, or a salt thereof. <3> m1 is 2 <2> a compound, a tautomer thereof, or a salt thereof <4> The bonding position of X- is meta to the hydroxy group <1> ~ <3> 1. A compound according to any one of the above, a tautomer thereof, or a salt thereof. <5> R is a halogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, a carboxy group, a carbamoyl group, a cyano group, an acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfo group. <1> ~ <4> 1. A compound according to any one of the above, a tautomer thereof, or a salt thereof. <6> At least one of Ar is a group represented by any one of the following formulas (A-1) to (A-28): <1> ~ <3> 1. A compound according to any one of the above, a tautomer thereof, or a salt thereof.

[0012] [ka]

[0013] [ka]

[0014] [ka]

[0015] In formulas (A-1) to (A-28), * represents the position at which the azo group in formula (1) is bonded, and R 21 ~R 27 , R 29 , R 31 and R 33 ~R 53 each independently represents a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclicthio group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group; R 28 , R 30 and R 32 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclicthio group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group; R 21 ~R 53 adjacent groups among these may bond to each other to form a saturated or unsaturated 5- or 6-membered ring structure, a, p, q, r, and s represent integers of 0 to 4, b and c represent integers of 0 to 6, d, e, f, g, t, and u represent integers of 0 to 3, h, i, j, k, l, and o represent integers of 0 to 2, w represents an integer of 0 to 5, m represents 0 or 1, and R 21 ~R53 The two or more groups represented by the formula may be the same or different.

[0016] <6> It is a bisazo dye <1> ~ <5> A compound according to any one of the above, a tautomer thereof, or a salt thereof. <7> <1> ~ <5> A coloring composition comprising any one of the compounds, tautomers thereof, or salts thereof. <8> Further comprising an aqueous solvent <7> The coloring composition according to claim 1. <9> <7> or <8> A dyeing method using the coloring composition described in 1. <10> <1> ~ <5> 1. A dyed article comprising the compound according to any one of the above, a tautomer thereof, or a salt thereof. <11> The method includes a step of reacting a diazonium salt represented by the following formula 5' with a compound represented by the following formula 6 to obtain a compound represented by the following formula 7': <1> ~ <6> A method for producing the compound, its tautomer, or a salt thereof according to any one of the above.

[0017] [ka]

[0018] In Formula 5', Formula 6 and Formula 7', Ar 11 represents a heterocyclic group, R represents a substituent, and X- represents R 1 O-, R 2a R 2b N- or R 3 S- represents R 1 , R 2a and R 2b each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, n represents 0, 1, 2 or 3, and when n represents 2 or 3, R may be the same or different.

[0019] <12> The method includes a step of reacting a diazonium salt represented by the following formula 5 with a compound represented by the following formula 6 to obtain a compound represented by the following formula 7, and a step of reacting the obtained compound represented by the formula 7 with a diazonium salt represented by the following formula 8. <1> ~ <6> A method for producing the compound, its tautomer, or a salt thereof according to any one of the above.

[0020] [ka]

[0021] In formulas 5 to 8, Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon group or a heterocyclic group, R represents a substituent, and X- represents R 1 O-, R 2a R 2b N- or R 3 S- represents R 1 , R 2a and R 2b each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, n represents 0, 1 or 2, and when n represents 2, R may be the same or different. 1 and Ar 2 and cannot simultaneously be an aromatic hydrocarbon group.

[0022] <13> The method includes a step of reacting a diazonium salt represented by the following formula 5 with a compound represented by the following formula 10 to obtain a compound represented by the following formula 11, and a step of reacting the obtained compound represented by the formula 11 with a diazonium salt represented by the following formula 8 to obtain a compound represented by the following formula 12. <1> ~ <6> A method for producing the compound, its tautomer, or a salt thereof according to any one of the above.

[0023] [ka]

[0024] In Formula 5, Formula 8, and Formulas 10 to 12, Ar 1 and Ar 2each independently represents an aromatic hydrocarbon group or a heterocyclic group, R represents a substituent, n1 represents 0, 1 or 2, and when n1 represents 2, R may be the same or different. 1 and Ar 2 and cannot simultaneously be an aromatic hydrocarbon group.

[0025] <14> The method includes a step of reacting a diazonium salt represented by the following formula 5 with a compound represented by the following formula 13 to obtain a compound represented by the following formula 14, and a step of reacting the obtained compound represented by formula 14 with a diazonium salt represented by the following formula 8 to obtain a compound represented by the following formula 15. <1> ~ <6> A method for producing the compound, its tautomer, or a salt thereof according to any one of the above.

[0026] [ka]

[0027] In Formula 5, Formula 8 and Formulas 13 to 15, Ar 1 and Ar 2 R each independently represents an aromatic hydrocarbon group or a heterocyclic group. 2a and R 2b each independently represents a hydrogen atom or an alkyl group, R 2a and R 2b may be the same or different, and R 2a and R 2b may bond to form a nitrogen-containing heterocycle. R represents a substituent, n1 represents 0, 1, 2 or 3, and when n1 represents 2 or 3, R may be the same or different. However, Ar 1 and Ar 2 and cannot simultaneously be an aromatic hydrocarbon group. [Effects of the Invention]

[0028] According to an embodiment of the present invention, a novel compound, a tautomer thereof, or a salt thereof can be provided. According to another embodiment of the present invention, a coloring composition having a low saturation hue can be provided. Furthermore, according to still another embodiment of the present invention, there can be provided a method for producing the above-mentioned compound, its tautomer, or a salt thereof, as well as a dyeing method and a dyed product dyed with the above-mentioned compound, its tautomer, or a salt thereof. DETAILED DESCRIPTION OF THE INVENTION

[0029] The present disclosure will be described in detail below. The following description of the components may be based on representative embodiments of the present disclosure, but the present disclosure is not limited to such embodiments. In this specification, the use of "to" to indicate a range of values ​​means that the values ​​before and after it are included as the lower and upper limits. In the present specification, the upper or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range. In addition, in the present specification, the upper or lower limit of a numerical range may be replaced with a value shown in the examples. Furthermore, in the description of groups (atomic groups) in this specification, a description that does not specify whether it is substituted or unsubstituted includes both unsubstituted and substituted groups. For example, the term "alkyl group" includes not only alkyl groups that do not have a substituent (unsubstituted alkyl groups) but also alkyl groups that have a substituent (substituted alkyl groups). Furthermore, the term "step" in this specification does not only refer to an independent step, but also includes a step that cannot be clearly distinguished from other steps as long as the intended purpose of the step is achieved. Furthermore, in this disclosure, "% by mass" and "% by weight" are synonymous, and "parts by mass" and "parts by weight" are synonymous. Furthermore, in the present disclosure, a combination of two or more preferred embodiments is a more preferred embodiment. The present disclosure will be described in detail below.

[0030] (Compounds represented by formula 1, their tautomers, or salts thereof) The compound, tautomer, or salt thereof according to the present disclosure is a compound represented by formula 1, a tautomer, or salt thereof. Certain embodiments of the compound represented by formula 1 according to the present disclosure, its tautomer, or a salt thereof can be suitably used as an azo dye. Furthermore, certain embodiments of the compound represented by formula 1 according to the present disclosure, its tautomer, or a salt thereof can be suitably used as a bisazo dye. The present disclosure includes not only compounds represented by Formula 1, but also tautomers thereof. The compound represented by formula 1 or a tautomer thereof may be in the form of a salt, or may be a mixed salt of two or more kinds. Tautomers are, for example, commonly known isomers in which a compound exists as two or more isomers that can be easily converted from one to the other, such as isomers that are generated when a proton bonded to one atom in a molecule moves to another atom.

[0031] [ka]

[0032] In Formula 1, X- represents R 1 O-, R 2a R 2b N- or R 3 S- represents R 1 , R 2a and R 2b each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group. X- is R 2a R 2b If N-, R 2a and R 2b may be the same or different, and R 2a and R 2bmay bond to form a nitrogen-containing heterocycle. Each R independently represents a substituent, n represents 0, 1, 2, or 3, and when n represents 2 or 3, the Rs may be the same or different. Ar represents an aromatic hydrocarbon group or a heterocyclic group, m1 represents 1, 2, or 3, and when m1 represents 2 or 3, the Ars may be the same or different, provided that at least one Ar is a heterocyclic group.

[0033] As a result of extensive investigations, the present inventors have found that by adopting the structure of the compound represented by the above formula 1, it is possible to provide a novel compound, its tautomer, or a salt thereof. Furthermore, as a result of extensive research, the present inventors have found that by adopting the above-mentioned configuration, it is possible to provide a compound, a colored composition, and a colored product that have a hue with low chroma. The mechanism of action of the excellent effects of the above-mentioned constitution is not clear, but is presumed as follows. The compound represented by the above formula 1, its tautomer, or a salt thereof may have a phenol structure, an X-structure (i.e., R 1 O-structure, R 2a R 2b N-structure or R 3 The presence of an azo group (S-structure), and at least one heterocyclic group linked to the azo group results in a compound with low chroma. Furthermore, dissociation of the phenol structure (forming a phenoxide structure) results in a compound with even lower chroma.

[0034] Furthermore, the compound represented by the above formula 1, its tautomer, or a salt thereof, when configured as described above, is estimated to have a low brightness hue, excellent hue fastness, and a wide absorption waveform across the entire visible range (wavelengths of 400 nm to 700 nm).

[0035] The compound represented by formula 1, its tautomer, or a salt thereof will be described in detail below.

[0036] In Formula 1, Ar represents an aromatic hydrocarbon group or a heterocyclic group. When m1 in Formula 1 represents 2 or 3, Ar may be the same or different, provided that at least one of Ar is a heterocyclic group. Each Ar is preferably a heterocyclic group from the viewpoints of low saturation, low brightness, and broad absorption in the visible range. The aromatic hydrocarbon group for Ar may be unsubstituted or may have a substituent. The aromatic hydrocarbon group which may have a substituent is preferably a phenyl group, a 1-naphthyl group, or a 2-naphthyl group. The heterocyclic group for Ar is preferably a heterocyclic group containing one or more heteroatoms selected from the group consisting of oxygen atoms, sulfur atoms, and nitrogen atoms in the ring, from the viewpoint of having low saturation, low brightness, and broad absorption in the visible region. From the viewpoint of low saturation, low brightness, and broad absorption in the visible region, the heterocyclic group for Ar is preferably a heterocyclic group containing a 5-membered heterocycle or a 6-membered heterocycle, more preferably a heterocyclic group containing a 5-membered heterocycle, and particularly preferably a 5-membered heteroaromatic ring. Furthermore, from the viewpoint of low saturation, low brightness, and broad absorption in the visible region, the heterocyclic group for Ar is preferably a heteroaromatic ring group, and more preferably a 5- or 6-membered heterocyclic group containing one or more heteroatoms selected from the group consisting of oxygen atoms, sulfur atoms, and nitrogen atoms in the ring. Furthermore, from the viewpoint of low saturation, low brightness, and broad absorption in the visible region, the heterocyclic group for Ar is preferably a heterocyclic group containing a sulfur atom, more preferably a heterocyclic group containing a sulfur atom and a nitrogen atom, and particularly preferably a heteroaromatic group containing a sulfur atom and a nitrogen atom. The heterocyclic group in Ar may be a ring fused with another ring. Among such fused ring groups, those fused with a 5-membered or 6-membered ring are preferred. The heterocyclic group for Ar preferably has 2 to 20 carbon atoms, and more preferably 2 to 10 carbon atoms. The number of heteroatoms in the heterocyclic group in Ar is preferably 2 or more, more preferably 2 to 4, and particularly preferably 2 or 3, from the viewpoint of low saturation, low brightness, and broad absorption in the visible range. Furthermore, when there are two or more Ar, each Ar may be the same group (when at least two are heterocyclic groups) or different groups, but from the viewpoint of low saturation, low brightness, and broad absorption in the visible range, it is preferable that the Ar be different groups.

[0037] The heterocyclic group in Ar in Formula 1 is preferably one derived from a diazo component. Here, the diazo component refers to a partial structure that can be introduced by converting a heterocyclic compound having an amino group as a substituent into a diazo compound and then subjecting the diazo compound to a diazo coupling reaction with a coupler (for example, the phenol structure moiety in Formula 1). In other words, the heterocyclic group in Ar is a substituent that is obtained by removing the amino group from an amino-substituted heterocyclic compound that is capable of undergoing a diazotization reaction, resulting in a monovalent group.

[0038] The aromatic hydrocarbon group and heterocyclic group in Ar in formula 1 can contain one or more substituents, and the two or more substituents may be the same or different. Examples of the substituent include a halogen atom, a hydroxy group, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, a heterocyclic group, an alkoxy group, an aryloxy group, a heterocyclic oxy group, a sulfo group, an acyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, a carboxy group, a carbamoyl group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a cyano group, a nitro group, an amino group (including an anilino group), an acylamino group, ...alkoxycarbonyl group, an aryloxycarbonyl group, a carboxy group, a carbamoyl group, an acyloxy group, a carbamoyloxy group, an alkoxycarbonyloxy group, an aryloxycarbonyloxy group, a cyano group, a nitro group, an amino group (including an anilino group), an acylamino group, an acylamino group, an acylamino group, an acylamino group, an acylamino group, an Examples of the alkyl group include an alkyl group, an alkoxycarbonylamino group, a carbamoylamino group, an aryloxycarbonylamino group, a sulfamoylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, a mercapto group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, an arylazo group, a heterocyclic azo group, an imido group, a phosphino group, a phosphinyl group, a phosphinyloxy group, and a phosphinylamino group. More specifically, examples of the substituent include a halogen atom (e.g., a fluorine atom, a chlorine atom, a bromine atom, an iodine atom), an alkyl group (a linear, branched, or cyclic alkyl group having 1 to 10, preferably 1 to 6, carbon atoms, such as methyl, ethyl, n-propyl, isopropyl, t-butyl, n-octyl-2-chloroethyl-2-cyanoethyl-2-ethylhexyl, cyclopropyl, and cyclopentyl), and an alkenyl group (a linear, branched, or cyclic alkenyl group having 2 to 10, preferably 2 to 6, carbon atoms, such as vinyl, allyl, prenyl, and cyclopenten-1-yl). , alkynyl groups (alkynyl groups having 2 to 10, preferably 2 to 6 carbon atoms, such as ethynyl and propargyl), aryl groups (aryl groups having 6 to 12, preferably 6 to 8 carbon atoms, such as phenyl, p-tolyl, naphthyl, 3-chlorophenyl and 2-aminophenyl), heterocyclic groups (monovalent groups having 1 to 12, preferably 2 to 6 carbon atoms, obtained by removing one hydrogen atom from a 5- or 6-membered aromatic or non-aromatic heterocyclic compound, such as 1-pyrazolyl, 1-imidazolyl, 2-furyl, 2-thienyl and 4-pyrimidinyl,2-benzothiazolyl), cyano group, hydroxy group, nitro group, alkoxy group (a linear, branched or cyclic alkoxy group having 1 to 10, preferably 1 to 6 carbon atoms, for example, methoxy, ethoxy, isopropoxy, t-butoxy, cyclopentyloxy, 2-buten-1-yloxy, 2-methoxyethoxy), aryloxy group (an aryloxy group having 6 to 12, preferably 6 to 8 carbon atoms, for example, phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy), heterocyclic oxy group (1 to 12, preferably Preferably, the heterocyclic group is a heterocyclic oxy group having 2 to 6 carbon atoms, such as 1-phenyltetrazol-5-oxy-2-tetrahydropyranyloxy), an acyloxy group (an acyloxy group having 1 to 12, preferably 1 to 8, carbon atoms, such as formyloxy, acetyloxy, pivaloyloxy, benzoyloxy, or p-methoxyphenylcarbonyloxy), a carbamoyloxy group (a carbamoyloxy group having 1 to 10, preferably 1 to 6, carbon atoms, such as N,N-dimethylcarbamoyloxy or N,N-diethylcarbamoyloxy), oxy, morpholinocarbonyloxy, N,N-octylcarbamoyloxy), alkoxycarbonyloxy groups (alkoxycarbonyloxy groups having 2 to 10, preferably 2 to 6, carbon atoms, for example, methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octyloxycarbonyloxy), aryloxycarbonyloxy groups (aryloxycarbonyloxy groups having 7 to 12, preferably 7 to 10, carbon atoms, for example, phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, nyloxy), amino groups (amino groups, alkylamino groups having 1 to 10, preferably 1 to 6 carbon atoms, an anilino group having 6 to 12, preferably 6 to 8 carbon atoms, or heterocyclic amino groups having 1 to 12, preferably 2 to 6 carbon atoms, such as amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, imidazol-2-ylamino, and pyrazol-3-ylamino), acylamino groups (alkylcarbonylamino groups having 1 to 10, preferably 1 to 6 carbon atoms,an arylcarbonylamino group having 6 to 12, preferably 6 to 8, carbon atoms, or a heterocyclic carbonylamino group having 2 to 12, preferably 2 to 6, carbon atoms, such as formylamino, acetylamino, pivaloylamino, benzoylamino, pyridine-4-carbonylamino, and thiophene-2-carbonylamino; an aminocarbonylamino group (an aminocarbonylamino group having 1 to 12, preferably 1 to 6, carbon atoms, such as carbamoylamino, N,N-dimethylaminocarbonylamino, and N,N-diethylaminocarbonylamino); aminocarbonylamino, morpholin-4-ylcarbonylamino), alkoxycarbonylamino groups (alkoxycarbonylamino groups having 2 to 10, preferably 2 to 6, carbon atoms, for example, methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino), aryloxycarbonylamino groups (aryloxycarbonylamino groups having 7 to 12, preferably 7 to 9, carbon atoms, for example, phenoxycarbonylamino, p-chlorophenoxycarbonylamino, 4-methoxyphenoxycarbonylamino), sulfamoylamino groups (sulfamoylamino groups having 0 to 10, preferably 0 to 6, carbon atoms, for example, sulfamoylamino, N,N-dimethylaminosulfonylamino, N-(2-hydroxyethyl)sulfamoylamino), alkylsulfonylamino groups (alkylsulfonylamino groups having 1 to 10, preferably 1 to 6, carbon atoms, for example, methylsulfonylamino, butylsulfonylamino), arylsulfonylamino groups (arylsulfonylamino groups having 6 to 12, preferably 6 to 8, carbon atoms, for example, methylsulfonylamino, butylsulfonylamino), groups, for example, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto groups, alkylthio groups (alkylthio groups having 1 to 10, preferably 1 to 6 carbon atoms, for example, methylthio, ethylthio, butylthio), arylthio groups (arylthio groups having 6 to 12, preferably 6 to 8 carbon atoms, for example, phenylthio, p-chlorophenylthio, m-methoxythio), heterocyclic thio groups (heterocyclic thio groups having 2 to 10, preferably 1 to 6 carbon atoms,For example, 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio), sulfamoyl groups (sulfamoyl groups having 0 to 10, preferably 0 to 6 carbon atoms, for example, sulfamoyl, N-ethylsulfamoyl, N,N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl), alkylsulfinyl groups (alkylsulfinyl groups having 1 to 10, preferably 1 to 6 carbon atoms, for example, methylsulfinyl, ethylsulfinyl), arylsulfinyl groups (6 to 12, preferably 1 to 6 carbon atoms, for example, methylsulfinyl, ethylsulfinyl), Preferably, an arylsulfinyl group having 6 to 8 carbon atoms, for example, phenylsulfinyl, p-methylphenylsulfinyl, an alkylsulfonyl group (an alkylsulfonyl group having 1 to 10, preferably 1 to 6 carbon atoms, for example, methylsulfonyl, ethylsulfonyl), an arylsulfonyl group (an arylsulfonyl group having 6 to 12, preferably 6 to 8 carbon atoms, for example, phenylsulfonyl, p-chlorophenylsulfonyl), a sulfo group, an acyl group (a formyl group having 2 to 10, preferably 2 to 6 carbon atoms, or an arylcarbonyl group having 7 to 12, preferably 7 to 9 carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, benzoyl, and 2,4-dichlorobenzoyl; an alkoxycarbonyl group (an alkoxycarbonyl group having 2 to 10, preferably 2 to 6 carbon atoms, such as methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, and isobutyloxycarbonyl); an aryloxycarbonyl group (an aryloxy group having 7 to 12, preferably 7 to 9 carbon atoms, such as methyl, ... a dicarbonyl group, for example, phenoxycarbonyl-2-chlorophenoxycarbonyl, 3-nitrophenoxycarbonyl, 4-t-butylphenoxycarbonyl), a carbamoyl group (a carbamoyl group having 1 to 10, preferably 1 to 6, carbon atoms, for example, carbamoyl, N-methylcarbamoyl, N,N-dimethylcarbamoyl, N-(2-hydroxyethyl)carbamoyl, N-(methylsulfonyl)carbamoyl), an arylazo group (an arylazo group having 6 to 12, preferably 6 to 8, carbon atoms, for example, phenylazo,p-chlorophenylazo), heterocyclic azo groups (heterocyclic azo groups having 1 to 10, preferably 1 to 6 carbon atoms, for example, pyrazol-3-ylazo, thiazol-2-ylazo, 5-methylthio-1,3,4-thiadiazol-2-ylazo), imido groups (imido groups having 2 to 10, preferably 4 to 8 carbon atoms, for example, succinimide, phthalimide), phosphino groups (phosphino groups having 2 to 12, preferably 2 to 6 carbon atoms, for example, dimethylphosphino, diphenylphosphino, methylphenoxyphosphino, ), phosphinyl groups (phosphinyl groups having 2 to 12 carbon atoms, preferably 2 to 6 carbon atoms, such as phosphinyl and diethoxyphosphinyl), phosphinyloxy groups (phosphinyloxy groups having 2 to 12, preferably 2 to 6 carbon atoms, such as diphenoxyphosphinyloxy and dibutoxyphosphinyloxy), and phosphinylamino groups (phosphinylamino groups having 2 to 12, preferably 2 to 6 carbon atoms, such as dimethoxyphosphinylamino and dimethylaminophosphinylamino).

[0039] When these groups can be further substituted, they can further contain a substituent, and preferred examples of the substituent include groups having the same meanings as those described as preferred substituents of the heterocyclic group for Ar. When these groups are substituted with two or more substituents, these substituents may be the same or different.

[0040] The substituents of the aromatic hydrocarbon group and heterocyclic group in Ar in formula 1 are preferably halogen atoms, alkyl groups, aryl groups, heterocyclic groups, cyano groups, hydroxy groups, nitro groups, alkoxy groups, aryloxy groups, amino groups (including anilino groups), acylamino groups, aminocarbonylamino groups, alkoxycarbonylamino groups, alkylsulfonylamino groups, arylsulfonylamino groups, alkylthio groups, arylthio groups, heterocyclicthio groups, sulfamoyl groups, alkylsulfonyl groups, arylsulfonyl groups, acyl groups, alkoxycarbonyl groups, and carbamoyl groups, and more preferably halogen atoms, alkyl groups, cyano groups, hydroxy groups, nitro groups, alkoxy groups, amino groups (including anilino groups), acylamino groups, alkylsulfonylamino groups, and carbamoyl groups.

[0041] From the viewpoint of low saturation, low brightness, fastness of hue, and broad absorption in the visible range, at least one of Ar is preferably a group represented by any one of the following formulas (A-1) to (A-28). From the viewpoint of low saturation, low brightness, fastness of hue, and broad absorption in the visible region, it is preferable that at least one of Ar is a group represented by any one of the following formulas (A-1) to (A-28), and the following formulas (A-1), (A-5), (A-8), (A-9), (A-10), (A-11), (A-12), (A-13), (A-14), (A-15), (A-16), (A-17), (A-18), (A-19), (A-20), (A-21), (A-22), (A-23), (A-24), (A-25), (A-26), (A-27), (A-28), (A-29), (A-30), (A-31), (A-32), (A-33), (A-34), (A-35), (A-36), (A-37), (A-38), (A-39), (A-40), (A-41), (A-42), (A-43), (A-44), (A-45), (A-46), (A-47), (A-48), (A-49), (A-50), (A-51), (A-52), (A-53), (A-54), (A-55), (A-56), (A-57), (A-58), (A-59), (A-60), (A-61), (A-62), (A-63), (A-64), (A-65), (A-66), (A-67), (A-68), (A-69), (A-70), (A-71), (A-72), (A-73), (A-74), (A-75), (A-76), (A-77), (A-78), (A-79), (A-80), -15), formula (A-17), formula (A-19), formula (A-22), formula (A-23), formula (A-24) or formula (A-25), and particularly preferably a group represented by the following formula (A-8), formula (A-9), formula (A-10), formula (A-11), formula (A-14), formula (A-15), formula (A-22), formula (A-23) or formula (A-27).

[0042] [ka]

[0043] [ka]

[0044] [ka]

[0045] In formulas (A-1) to (A-28), * represents the position at which the azo group in formula 1 is bonded, and R 21 ~R 27 , R 29 , R 31 and R 33 ~R 53 each independently represents a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclicthio group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group; R 28 , R 30 and R 32 each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclicthio group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group; R 21 ~R 53 adjacent groups among these may bond to each other to form a saturated or unsaturated 5- or 6-membered ring structure, a, p, q, r, and s represent integers of 0 to 4, b and c represent integers of 0 to 6, d, e, f, g, t, and u represent integers of 0 to 3, h, i, j, k, l, and o represent integers of 0 to 2, w represents an integer of 0 to 5, m represents 0 or 1, and R 21 ~R 53 The two or more groups represented by the formula may be the same or different.

[0046] R 21 ~R 53 is a group that can be further substituted, R 21 ~R 53 may further contain a substituent, in which case the substituent is the same as those listed as the substituents of the heterocyclic group in Ar in Formula 1.

[0047] From the viewpoints of low saturation, low brightness, hue fastness, and broad absorption in the visible range, R in Formula 1 is preferably a halogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, a carboxy group, a carbamoyl group, a cyano group, an acylamino group, a sulfonylamino group, a sulfamoyl group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfo group, more preferably a halogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, or a carboxy group, and particularly preferably a hydroxy group, an alkyl group, or an acyl group. The halogen atom represented by R is, for example, preferably a fluorine atom, a chlorine atom, a bromine atom, or an iodine atom, and particularly preferably a fluorine atom or a chlorine atom. The alkyl group represented by R is preferably an alkyl group having 1 to 12 carbon atoms, and particularly preferably an alkyl group having 1 to 8 carbon atoms. For example, a methyl group, an ethyl group, an n-butyl group, or a t-butyl group is preferred. The aryl group represented by R is preferably an aryl group having 6 to 12 carbon atoms, such as a phenyl group, a 1-naphthyl group, or a 2-naphthyl group. The alkoxy group represented by R is preferably an alkoxy group having 1 to 12 carbon atoms, and more preferably an alkoxy group having 1 to 8 carbon atoms. For example, a methoxy group, an ethoxy group, an n-butoxy group, a t-butoxy group, or a 2-methoxyethoxy group is preferred. The aryloxy group represented by R is preferably an aryloxy group having 6 to 12 carbon atoms, for example, a phenoxy group or a 4-methylphenoxy group. The acyl group represented by R is preferably an acyl group having 1 to 12 carbon atoms, and particularly preferably an acyl group having 1 to 7 carbon atoms. For example, a formyl group, an acetyl group, a hydroxyacetyl group, a propionyl group, a 2-methylpropionyl group, or a benzoyl group is preferred. The alkoxycarbonyl group represented by R is preferably an alkoxycarbonyl group having 2 to 10 carbon atoms, and particularly preferably an alkoxycarbonyl group having 2 to 6 carbon atoms. For example, a methoxycarbonyl group, an ethoxycarbonyl group, a t-butoxycarbonyl group, or an isobutyloxycarbonyl group is preferred.

[0048] The carbamoyl group represented by R is preferably a carbamoyl group having 1 to 10 carbon atoms, and particularly preferably a carbamoyl group having 1 to 6 carbon atoms. For example, a carbamoyl group, an N-methylcarbamoyl group, an N,N-dimethylcarbamoyl group, an N-(2-hydroxyethyl)carbamoyl group, or an N-(methylsulfonyl)carbamoyl group is preferred. In the acylamino group represented by R, the alkylcarbonylamino group is preferably an alkylcarbonylamino group having 1 to 10 carbon atoms, and more preferably an alkylcarbonylamino group having 1 to 6 carbon atoms. Furthermore, the arylcarbonylamino group is preferably an arylcarbonylamino group having 6 to 12 carbon atoms, and more preferably an arylcarbonylamino group having 6 to 8 carbon atoms. Alternatively, the heterocyclic carbonylamino group is preferably a heterocyclic carbonylamino group having 2 to 12 carbon atoms, and more preferably a heterocyclic carbonylamino group having 2 to 6 carbon atoms. For example, a formylamino group, an acetylamino group, a pivaloylamino group, a benzoylamino group, a pyridine-4-carbonylamino group, or a thiophene-2-carbonylamino group is preferred. The sulfonylamino group represented by R is preferably an alkylsulfonylamino group having 1 to 10 carbon atoms, more preferably an alkylsulfonylamino group having 1 to 6 carbon atoms. Furthermore, the arylsulfonylamino group is preferably an arylsulfonylamino group having 6 to 12 carbon atoms, more preferably an arylsulfonylamino group having 6 to 8 carbon atoms. For example, a methylsulfonylamino group, a butylsulfonylamino group, a phenylsulfonylamino group, a 2,3,5-trichlorophenylsulfonylamino group, or a p-methylphenylsulfonylamino group is preferred. The sulfamoyl group represented by R is preferably a sulfamoyl group having 0 to 10 carbon atoms, and particularly preferably a sulfamoyl group having 0 to 6 carbon atoms. For example, a sulfamoyl group, an N-ethylsulfamoyl group, an N,N-dimethylsulfamoyl group, an N-acetylsulfamoyl group, or an N-benzoylsulfamoyl group is preferred. The alkylthio group represented by R is preferably an alkylthio group having 1 to 10 carbon atoms, and particularly preferably an alkylthio group having 1 to 6 carbon atoms. For example, a methylthio group, an ethylthio group, or a butylthio group is preferred. The arylthio group represented by R is preferably an arylthio group having 6 to 12 carbon atoms, and particularly preferably an arylthio group having 6 to 8 carbon atoms. For example, a phenylthio group, a p-chlorophenylthio group, or an m-methoxyphenylthio group is preferred. The alkylsulfonyl group represented by R is preferably an alkylsulfonyl group having 1 to 10 carbon atoms, and particularly preferably an alkylsulfonyl group having 1 to 6 carbon atoms. For example, a methylsulfonyl group or an ethylsulfonyl group is preferred. The arylsulfonyl group represented by R is preferably an arylsulfonyl group having 6 to 12 carbon atoms, and particularly preferably an arylsulfonyl group having 6 to 8 carbon atoms. For example, a phenylsulfonyl group or a p-chlorophenylsulfonyl group is preferred.

[0049] When n is 2, two R may be bonded to form a ring. The ring formed is preferably a 5- or 6-membered ring. The ring formed may be either saturated or unsaturated, but is preferably unsaturated. The ring formed may be either a hydrocarbon ring or a heterocyclic ring, but is preferably an aromatic hydrocarbon ring or a heteroaromatic ring. Examples of the ring formed include a cyclohexene ring, a benzene ring, a naphthalene ring, a pyrrole ring, and a pyrazole ring. A benzene ring or a pyrrole ring is particularly preferred.

[0050] In Formula 1, X- represents R 11 O-, R 2a R 2b N- or R 3 S- represents R 1 , R 2a and R 2b each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group. X- is R 2a R 2b If N-, R 2a and R 2b may be the same or different, and R 2a and R 2b may be bonded to form a nitrogen-containing heterocycle. In terms of low saturation and low brightness, X- is preferably R 11 O- and R 2a R 2b N- is more preferred.

[0051] R in Equation 1 1 , R 2a , R 2b or R 3 The alkyl group represented by the formula (I) is preferably an alkyl group having 1 to 12 carbon atoms, and particularly preferably an alkyl group having 1 to 4 carbon atoms. For example, a methyl group, an ethyl group, an n-butyl group, or a t-butyl group is preferred. R in Equation 1 1 , R 2a and R 2b is preferably a hydrogen atom or a methyl group from the viewpoints of low saturation, low brightness, water solubility, and broad absorption in the visible range.

[0052] X- is R 2a R2b R for N- 2a R 2b N- may be any of an amino group (H2N-), a monoalkyl-substituted amino group, and a dialkyl-substituted amino group. X- is R 2a R 2b N- represents R 2a and R 2b When these are bonded to form a nitrogen-containing heterocycle, the nitrogen-containing heterocycle is preferably a 5- or 6-membered nitrogen-containing heterocycle. Examples of the nitrogen-containing heterocycle include a pyrrolidine ring, a piperidine ring, a morpholine ring, and a piperazine ring.

[0053] In Formula 1, X- (i.e., R 1 O-, R 2a R 2b N- or R 3 The bonding position of S-) is not particularly limited, but from the viewpoints of low saturation, low brightness, fastness of hue, and broad absorption in the visible range, it is preferably the meta position relative to the hydroxy group.

[0054] In formula 1, m1 is preferably 2 or 3, and more preferably 2, from the viewpoints of low saturation, low brightness, fastness of hue, and broad absorption in the visible range. In formula 1, n is preferably 0, 1 or 2, and more preferably 0 or 1, from the viewpoints of low saturation, low brightness, fastness of hue, and broad absorption in the visible range.

[0055] When the compound represented by formula 1 forms a salt, it preferably forms a salt with a monovalent or divalent cation. Preferred monovalent cations are alkali metal cations (e.g., lithium cation, sodium cation, potassium cation) and ammonium cations (e.g., ammonium cation, trimethylammonium cation, triethylammonium cation, tetramethylammonium cation). Preferred divalent cations are alkaline earth metal cations (e.g., calcium cation).

[0056] The compound represented by formula 1 includes compounds represented by any of the following formulae A1 to A3.

[0057] [ka]

[0058] In Formula A1, X- represents R 1 O-, R 2a R 2b N- or R 3 S- represents R 1 , R 2a and R 2b each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, and X- represents R 2a R 2b If N-, R 2a and R 2b N- may be the same or different, and R 2a and R 2b may be bonded to form a nitrogen-containing heterocycle. 1 and Ar 2 each independently represents an aromatic hydrocarbon group or a heterocyclic group, and each R independently represents a substituent. n1 represents 0, 1, or 2, and when n1 represents 2, R may be the same or different. However, Ar 1 and Ar 2 and cannot simultaneously be an aromatic hydrocarbon group.

[0059] In Formula A2, X- represents R 1 O-, R 2a R 2b N- or R 3 S- represents R 1 , R 2a and R 2b each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, and X- represents R 2a R 2b If N-, R 2a and R 2b N- may be the same or different, R 2a and R 2bmay be bonded to form a nitrogen-containing heterocycle. n2 represents 0 or 1. Ar 1 , Ar 2 and Ar 3 each independently represents an aromatic hydrocarbon group or a heterocyclic group, provided that Ar 1 and Ar 2 and cannot simultaneously be an aromatic hydrocarbon group.

[0060] In Formula A3, X- represents R 1 O-, R 2a R 2b N- or R 3 S- represents R 1 , R 2a and R 2b each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, and X- represents R 2a R 2b If N-, R 2a and R 2b N- may be the same or different, R 2a and R 2b may be bonded to form a nitrogen-containing heterocycle. n3 represents 0, 1, 2, or 3, and when n3 represents 2 or 3, R may be the same or different. Ar 11 represents a heterocyclic group.

[0061] Ar in Formulas A1 to A3 1 , Ar 2 , Ar 3 and Ar 11 are each independently defined as Ar in formula 1, and preferred embodiments are also the same. R and R in Equation 1 2a and R 2b are R and R in Equation 1, respectively. 2a and R 2b The same applies to the preferred embodiments.

[0062] In formula A1, n1 is preferably 0 or 1 from the viewpoint of low saturation, low brightness, fastness of hue, and broad absorption in the visible range. In formula A2, n2 is preferably 0 from the viewpoint of low saturation, low brightness, fastness of hue, and broad absorption in the visible range. In formula A2, n2 is preferably 0, 1, or 2, more preferably 0 or 1, and even more preferably 0, from the viewpoint of low saturation, low brightness, fastness of hue, and broad absorption in the visible range.

[0063] From the viewpoint of low saturation, low brightness, hue fastness, and broad absorption in the visible range, the compound represented by Formula 1 is preferably a compound represented by any one of the following Formulae A1-1 to A1-3, A2-1 to A2-3, and A3-1 to A3-3, more preferably a compound represented by any one of the following Formulae A1-1 to A1-3 and A2-1 to A2-3, and even more preferably a compound represented by any one of the following Formulae A1-1, A1-2, and A1-3.

[0064] [ka]

[0065] In Formula A1-1 to Formula A1-3, X- represents R 1 O-, R 2a R 2b N- or R 3 S- represents R 1 , R 2a and R 2b each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, and X- represents R 2a R 2b If N-, R 2a and R 2b N- may be the same or different, R 2a and R 2b may be bonded to form a nitrogen-containing heterocycle. 1 and Ar 2each independently represents an aromatic hydrocarbon group or a heterocyclic group, and each R independently represents a substituent. n1 represents 0, 1, or 2, and when n1 represents 2, R may be the same or different. However, Ar 1 and Ar 2 and cannot simultaneously be an aromatic hydrocarbon group.

[0066] In formulas A2-1 to A2-3, X- is R 1 O-, R 2a R 2b N- or R 3 S- represents R 1 , R 2a and R 2b each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, and X- represents R 2a R 2b If N-, R 2a and R 2b N- may be the same or different, R 2a and R 2b may be bonded to form a nitrogen-containing heterocycle. n1 represents 0 or 1. Ar 1 , Ar 2 and Ar 3 each independently represents an aromatic hydrocarbon group or a heterocyclic group, provided that Ar 1 and Ar 2 and cannot simultaneously be an aromatic hydrocarbon group.

[0067] In Formula A3-1 to Formula A3-3, X- is R 1 O-, R 2a R 2b N- or R 3 S- represents R 1 , R 2a and R 2b each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, and X- represents R 2a R 2b If N-, R 2a and R 2b N- may be the same or different, R 2a and R 2bmay be bonded to form a nitrogen-containing heterocycle. n3 represents 0, 1, 2, or 3, and when n3 represents 2 or 3, R may be the same or different. Ar 11 represents a heterocyclic group.

[0068] Ar in Formulas A1-1 to A1-3 1 , Ar 2 , R, R 1 , R 2a , R 2b , R 3 and n1 are Ar in formula A1, respectively. 1 , Ar 2 , R, R 2a , R 2b , R 3 and n1, and the preferred embodiments are also the same. Ar in Formula A2-1 to Formula A2-3 1 , Ar 2 , Ar 3 , R 1 , R 2a , R 2b , R 3 and n2 are Ar in formula A2, respectively. 1 , Ar 2 , Ar 3 , R 1 , R 2a , R 2b , and R 3 The same applies to the preferred embodiments. Ar in Formulas A3-1 to A3-3 11 , R 1 , R 2a , R 2b , R 3 and n3 are Ar in formula A3, respectively. 11 , R 1 , R 2a , R 2b , and R 3 The same applies to the preferred embodiments.

[0069] X- in formula A1 is R 1 When O- is represented, the compound represented by formula A1 is Ar 1 and Ar2 are each independently a heterocyclic group, and R 1 is preferably a hydrogen atom, R is a hydroxy group, an alkyl group, or an acyl group, and n1 is preferably 0 or 1; 1 is a heterocyclic group having a sulfur atom, and Ar 2 But, Ar 1 is a heterocyclic group different from R 1 is a hydrogen atom, R is a hydroxy group, an alkyl group, or an acyl group, and n1 is 0 or 1; 1 is a heterocyclic group having a sulfur atom and a nitrogen atom, and Ar 2 But, Ar 1 is a heterocyclic group different from R 1 It is particularly preferred that n is a hydrogen atom, R is a hydroxy group, an alkyl group, or an acyl group, and n1 is 0 or 1.

[0070] X- in formula A1 is R 2a R 2b When N- is represented, the compound represented by formula A1 is Ar 1 and Ar 2 are each independently a heterocyclic group, and R 2a and R 2b are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R 2a and R 2b When Ar is bonded to form a nitrogen-containing heterocycle, it is preferably a pyrrolidino group, a piperidino group, or a morpholino group, R is a halogen atom (e.g., a chlorine atom) or a methyl group, and n1 is 0 or 1; 1 is a 5-membered heterocyclic group or a 5- or 6-membered fused heterocyclic group, and Ar 2 is a 5-membered heterocyclic group, a 5- or 6-membered fused heterocyclic group, or an aromatic hydrocarbon group, and R 2a is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n-butyl group, or a t-butyl group), and R 2bis more preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n-butyl group, or a t-butyl group), R is a hydrogen atom or a methyl group, and n is 0 or 1; 1 is a 5-membered heterocyclic group or a 5- or 6-membered fused heterocyclic group, and Ar 2 is a 5-membered heterocyclic group or a 5- or 6-membered fused heterocyclic group, and R 2a is a hydrogen atom or a methyl group, and R 2b It is particularly preferred that R is a hydrogen atom or a methyl group, R is a chlorine atom or a methyl group, and n1 is 0 or 1.

[0071] X- in formula A1 is R 3 When S- is represented, the compound represented by formula A1 is Ar 1 and Ar 2 are each independently a heterocyclic group, and R 3 is preferably an alkyl group having 1 to 4 carbon atoms, R is a halogen atom (e.g., a chlorine atom) or a methyl group, and n1 is 0 or 1; 1 is a 5-membered heterocycle or a 5- or 6-membered fused heterocycle, and Ar 2 is a 5-membered heterocyclic group, a 5- or 6-membered fused heterocyclic group, or an aromatic hydrocarbon group, and R 3 is an alkyl group having 1 to 4 carbon atoms, R is a chlorine atom or a methyl group, and n1 is 0 or 1; 1 is a 5-membered heterocycle or a 5- or 6-membered fused heterocycle, and Ar 2 is a 5-membered heterocycle or a 5- or 6-membered fused heterocycle, and R 3 It is particularly preferred that R is a methyl group, R is a chlorine atom or a methyl group, and n1 is 0 or 1.

[0072] X- in formula A2 is R 1 When O- is represented, the compound represented by formula A2 is Ar 1 , Ar 2 , Ar 3 are each independently a heterocyclic group, and R1 is preferably a hydrogen atom, a methyl group, an ethyl group, or a hydroxyethyl group, R is a halogen atom (e.g., a chlorine atom) or a methyl group, and n2 is preferably 0 or 1; 1 is a 5-membered heterocycle or a 5- or 6-membered fused heterocycle, and Ar 2 is a 5-membered heterocycle or a 5- or 6-membered fused heterocycle, and Ar 3 is a 5-membered heterocyclic group, a 5- or 6-membered fused heterocyclic group, or an aromatic hydrocarbon group, and R 1 is preferably a hydrogen atom or a methyl group, R is preferably a chlorine atom or a methyl group, and n2 is preferably 0 or 1; 1 is a five-membered heterocycle, and Ar 2 is a 5-membered heterocycle or a 5- or 6-membered fused heterocycle, and Ar 3 is a 5-membered heterocycle or a 5- or 6-membered fused heterocycle, and R 1 is preferably a hydrogen atom or a methyl group, and n2 is preferably 0.

[0073] X- in formula A2 is R 2a R 2b When N- is represented, the compound represented by formula A2 is Ar 1 , Ar 2 , Ar 3 are each independently a heterocyclic group, and R 2a and R 2b are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R 2a and R 2b When R is bonded to form a nitrogen-containing heterocycle, it is preferably a pyrrolidino group, a piperidino group, or a morpholino group, R is a halogen atom (e.g., a chlorine atom) or a methyl group, and n2 is 0 or 1; 1 is a 5-membered heterocycle or a 5- or 6-membered fused heterocycle, and Ar 2 is a 5-membered heterocycle or a 5- or 6-membered fused heterocycle, and Ar 3 is a 5-membered heterocyclic group, a 5- or 6-membered fused heterocyclic group, or an aromatic hydrocarbon group, and R 2a is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n-butyl group, or a t-butyl group), and R2b is preferably a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (e.g., a methyl group, an ethyl group, an n-butyl group, or a t-butyl group), R is preferably a chlorine atom or a methyl group, and n2 is preferably 0 or 1; 1 is a 5-membered heterocyclic group, and Ar 2 is a 5-membered heterocyclic group or a 5- or 6-membered fused heterocyclic group, and Ar 3 is a 5-membered heterocyclic group or a 5- or 6-membered fused heterocyclic group, and R 2a is a hydrogen atom or a methyl group, and R 2b It is particularly preferred that n is a hydrogen atom or a methyl group and n2 is 0.

[0074] X- in formula A2 is R 3 When S- is represented, the compound represented by formula A1 is Ar 1 and Ar 2 , Ar 3 are each independently a heterocyclic group, and R 3 is preferably an alkyl group having 1 to 4 carbon atoms, R is a chlorine atom or a methyl group, and n2 is 0 or 1; 1 is a 5-membered heterocyclic group or a 5- or 6-membered fused heterocyclic group, and Ar 2 is a 5-membered heterocyclic group or a 5- or 6-membered fused heterocyclic group, and Ar 3 is a 5-membered heterocyclic group, a 5- or 6-membered fused heterocyclic group, or an aromatic hydrocarbon group, and R 3 is an alkyl group having 1 to 4 carbon atoms, R is a chlorine atom or a methyl group, and n2 is 0 or 1; 1 is a 5-membered heterocyclic group, and Ar 2 is a 5-membered heterocyclic group or a 5- or 6-membered fused heterocyclic group, and Ar 3 is a 5-membered heterocyclic group or a 5- or 6-membered fused heterocyclic group, and R 3 It is particularly preferred that n is a methyl group and n2 is 0.

[0075] X- in formula A3 is R 1When O- is represented, the compound represented by formula A3 is Ar 11 is a heterocyclic group, and R 1 is preferably a hydrogen atom, a methyl group, an ethyl group, or a hydroxyethyl group, R is a halogen atom (e.g., a chlorine atom) or a methyl group, and n3 is preferably 0 or 1; 11 is a 5-membered heterocyclic group or a 5- or 6-membered fused heterocyclic group, and R 1 is a hydrogen atom or a methyl group, R is a chlorine atom or a methyl group, and n3 is 0 or 1; 11 is a 5-membered heterocyclic group or a 5- or 6-membered fused heterocyclic group, and R 1 It is particularly preferred that n is a hydrogen atom or a methyl group and n3 is 0.

[0076] X- in formula A3 is R 2a R 2b When N- is represented, the compound represented by formula A3 is Ar 11 is a heterocyclic group, and R 2a and R 2b are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, and R 2a and R 2b When R is bonded to form a nitrogen-containing heterocycle, it is preferably a pyrrolidino group, a piperidino group, or a morpholino group, R is a chlorine atom or a methyl group, and n3 is 0 or 1; 11 is a 5-membered heterocyclic group or a 5- or 6-membered fused heterocyclic group, and R 2a is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n-butyl group, or a t-butyl group), and R 2b is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (for example, a methyl group, an ethyl group, an n-butyl group, or a t-butyl group), R is a chlorine atom or a methyl group, and n3 is 0 or 1; 11 is a 5-membered heterocyclic group or a 5- or 6-membered fused heterocyclic group, and R 2a is a hydrogen atom or a methyl group, and R 2bis a hydrogen atom or a methyl group, R is a chlorine atom or a methyl group, and n3 is 0 or 1.

[0077] X- in formula A3 is R 3 When S- is represented, the compound represented by formula A3 is Ar 11 is a heterocyclic group, and R 3 is preferably an alkyl group having 1 to 4 carbon atoms, R is a chlorine atom or a methyl group, and n3 is preferably 0 or 1; 11 is a 5-membered heterocyclic group or a 5- or 6-membered fused heterocyclic group, and R 3 is preferably an alkyl group having 1 to 4 carbon atoms, R is a chlorine atom or a methyl group, and n3 is preferably 0 or 1; 11 is a 5-membered heterocyclic group or a 5- or 6-membered fused heterocyclic group, and R 3 It is particularly preferred that n is a methyl group and n3 is 0.

[0078] Specific examples of the compound represented by formula 1 are listed below, but the present disclosure is not limited to these examples. Note that Me represents a methyl group, and Et represents an ethyl group (the same applies hereinafter).

[0079] [ka]

[0080] [ka]

[0081] [ka]

[0082] [ka]

[0083]

change

[0084]

change

[0085]

change

[0086]

change

[0087]

change

[0088]

change

[0089]

change

[0090]

change

[0091]

change

[0092]

change

[0093]

change

[0094] [ka]

[0095] The method for producing the compound represented by formula 1, its tautomers, and salts thereof is not particularly limited, and they can be synthesized, for example, by the method described in JP-A-2017-515930. In one embodiment of the method for producing the compound represented by formula 1, its tautomer, and salts thereof, it is preferable to include a step of reacting a diazonium salt represented by the following formula 5′ with a compound represented by the following formula 6 to obtain a compound represented by the following formula 7′ (also referred to as a “diazotization step 1′”).

[0096] [ka]

[0097] In Formula 5', Formula 6 and Formula 7', Ar 11 represents a heterocyclic group, R represents a substituent, and X- represents R 1 O-, R 2a R 2b N- or R 3 S- represents R 1 , R 2a and R 2b each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, n represents 0, 1, 2 or 3, and when n represents 2 or 3, R may be the same or different.

[0098] Furthermore, in one embodiment of the method for producing the compound represented by formula 1, its tautomer, and salts thereof, it is preferable to include a step (diazotization step 1) of reacting a diazonium salt represented by formula 5 below with a compound represented by formula 6 below to obtain a compound represented by formula 7 below, and a step (also referred to as "diazotization step 2") of reacting the obtained compound represented by formula 7 with a diazonium salt represented by formula 8 below. In other words, the method for producing the compound represented by formula 1, its tautomer, and salts thereof may include an embodiment in which a diazonium salt that is a compound represented by formula 7 is used as an intermediate and reacted with a diazonium salt represented by formula 8.

[0099] [ka]

[0100] In formulas 5 to 8, Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon group or a heterocyclic group, R represents a substituent, and X- represents R 1 O-, R 1 S- or R 1 R 2 N- represents R 1 and R 2 are each independently, R 1 and R 2 each independently represents a hydrogen atom or an alkyl group, n represents 0, 1, 2 or 3, and when n represents 2 or 3, R may be the same or different. 1 and Ar 2 and cannot simultaneously be an aromatic hydrocarbon group.

[0101] In one embodiment of the method for producing the compound represented by formula 1, its tautomer, and salts thereof, it is more preferable to include a step of reacting a diazonium salt represented by formula 5 below with a compound represented by formula 10 below to obtain a compound represented by formula 11 below (also referred to as "diazotization step 3"), and a step of reacting the obtained compound represented by formula 11 with a diazonium salt represented by formula 8 below to obtain a compound represented by formula 12 below (also referred to as "diazotization step 4").

[0102] [ka]

[0103] In Formula 5, Formula 8, and Formulas 10 to 12, Ar 1 and Ar 2 each independently represents an aromatic hydrocarbon group or a heterocyclic group, R represents a substituent, n1 represents 0, 1 or 2, and when n1 represents 2, R may be the same or different. 1 and Ar 2 and cannot simultaneously be an aromatic hydrocarbon group.

[0104] In addition, in one embodiment of the method for producing the compound represented by formula 1, its tautomer, and salts thereof, it is preferable to include a step of reacting a diazonium salt represented by formula 5 below with a compound represented by formula 13 below to obtain a compound represented by formula 14 below (also referred to as "diazotization step 5"), and a step of reacting the obtained compound represented by formula 14 with a diazonium salt represented by formula 8 below to obtain a compound represented by formula 15 below (also referred to as "diazotization step 6").

[0105] [ka]

[0106] In Formula 5, Formula 8 and Formulas 13 to 15, Ar 1 and Ar 2 R each independently represents an aromatic hydrocarbon group or a heterocyclic group. 1 and R 2 each independently represents a hydrogen atom or an alkyl group, R 1 and R 2 may be the same or different, and R 1 and R 2 may bond to form a nitrogen-containing heterocycle. R represents a substituent, n1 represents 0, 1 or 2, and when n represents 2, R may be the same or different. However, Ar 1 and Ar2 and cannot simultaneously be an aromatic hydrocarbon group.

[0107] Ar in Formula 5' and Formula 7' 11 has the same meaning as Ar in formula 1, and the preferred embodiments are also the same. Ar in Formula 5 and Formulas 7 to 8 1 and Ar 2 Each of these has the same meaning as Ar in formula 1, and the preferred embodiments are also the same. X-, R and n in formulae 6 to 7 and 7' have the same meanings as X-, R and n in formula 1, respectively, and the preferred embodiments are also the same. Ar in Equations 10 to 12 1 , Ar 2 , R, R 1 and n1 are Ar in formula A1, respectively. 1 , Ar 2 , R, R 1 and n1, and the preferred embodiments are also the same. Ar in Equations 13 to 15 1 , Ar 2 , R, R 2a and R 2a , n1 are Ar in formula A1 1 , Ar 2 , R, R 2a and R 2a , n1, and the preferred embodiments are also the same. The method for preparing the diazonium salt represented by formula 5', formula 5, or formula 8 is not particularly limited, and the salt may be prepared by a known method or by referring to a known method. Specifically, a suitable example is a method for preparing a diazonium salt by reacting the amino group of an amine compound with sodium nitrite or nitrosylsulfuric acid. The counter anion of the diazonium salt represented by formula 5 or 8 is not particularly limited, and any known anion can be used. In the above diazotization step 1' and diazotization steps 1 to 6, known diazo coupling reaction conditions (for example, reaction temperature, reaction time, reaction solvent, etc.) can be used. Furthermore, the molar ratio of the reaction substrates in the diazotization step 1' and the diazotization steps 1 to 6 is not particularly limited, and can be appropriately selected depending on the scarcity and reactivity of each reaction substrate.

[0108] <Application> The compound represented by Formula 1, its tautomer, and a salt thereof are preferably used as a coloring composition, and more preferably used as a coloring composition containing an aqueous solvent and the compound represented by Formula 1, its tautomer, or a salt thereof. Furthermore, the compound represented by Formula 1, its tautomer, and a salt thereof, or the coloring composition has a specific hue with low saturation, and therefore can be suitably used as a pigment, and more suitably used as a dye. Furthermore, applications of the compound represented by Formula 1, its tautomers, and salts thereof include black matrices used in displays such as liquid crystal displays (LCDs) and plasma display panels (PDPs), curable compositions for producing these black matrices, color image recording materials for forming color images, etc. Specific applications include inkjet recording materials (e.g., inkjet recording inks), dye-sublimation thermal recording materials, electrophotographic recording materials (e.g., color toners), transfer-type silver halide photosensitive materials, printing inks, recording pens, and textile dyeing, with preferred applications including inkjet recording materials, transfer-type silver halide photosensitive materials, printing inks, and textile dyeing. The compound represented by formula 1, its tautomer, or a salt thereof can be used by optimizing its physical properties such as solubility and dispersibility suitable for the intended use by adjusting the substituents. Furthermore, the compound represented by formula 1, its tautomer, or a salt thereof can be used in a dissolved state, an emulsified dispersion state, or a solid dispersion state depending on the system in which it is used.

[0109] (Colored composition) The coloring composition according to the present disclosure contains a compound represented by Formula 1, a tautomer thereof, or a salt thereof, and from the viewpoint of dyeing properties, it preferably further contains an aqueous solvent.

[0110] The coloring composition according to the present disclosure may contain one or more of the compound represented by Formula 1, its tautomer, or a salt thereof, and may also be combined with other direct dyes or disperse dyes.

[0111] The coloring composition according to the present disclosure may contain a medium. The coloring composition according to the present disclosure can be prepared by using a lipophilic medium and / or an aqueous medium as a medium and dissolving and / or dispersing at least one compound selected from the group consisting of the compound represented by Formula 1, its tautomers, and salts thereof in the medium. An aqueous medium is preferably used, and an aqueous solvent is more preferably used.

[0112] The contents of the compound represented by Formula 1, its tautomers, and salts thereof contained in the colored composition according to the present disclosure are determined depending on the types of substituents in the compound represented by Formula 1, its tautomers, and salts thereof used, and the type of solvent component used to produce the colored composition, and the like. The contents of the compound represented by Formula 1, its tautomers, and salts thereof in the colored composition are preferably 0.001% by mass to 30% by mass, more preferably 0.001% by mass to 20% by mass, even more preferably 0.1% by mass to 10% by mass, and particularly preferably 0.5% by mass to 10% by mass, relative to the total mass of the colored composition. By setting the content of the compound represented by Formula 1, its tautomer, and salts thereof to 0.001% by mass or more, the coloring density of the dye on a medium to be colored can be ensured. Furthermore, by setting the content of the compound represented by Formula 1, its tautomer, and salts thereof to 30% by mass or less, a coloring composition with low viscosity can be prepared, making it easy to handle.

[0113] When the coloring composition according to the present disclosure contains an aqueous solvent (preferably water), it can be used at any pH. From the viewpoints of the stability and dyeability of the compound, the pH is preferably in the range of 5 to 11, more preferably in the range of 6 to 11, and particularly preferably in the range of 7 to 11, from the viewpoints of the stability and dyeability of the compound represented by Formula 1, its tautomer, and a salt thereof. The pH values ​​in this disclosure are values ​​at 25°C.

[0114] The coloring composition according to the present disclosure may contain a pH adjuster. Examples of pH adjusters that can be used in the colored composition according to the present disclosure include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, potassium bicarbonate, ammonia, monoethanolamine, diethanolamine, and guanidine.

[0115] The coloring composition according to the present disclosure may contain a surfactant. Examples of surfactants that can be used include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric or zwitterionic surfactants. The surfactants may be used alone or in combination of two or more. Examples of anionic surfactants that can be used in the coloring composition according to the present disclosure include monoalkyl sulfuric acid or its salt, alkylbenzenesulfonic acid or its salt, and α-olefin sulfonate or its salt. In particular, sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, and alkali salts of sulfosuccinic acid half esters, such as disodium monooctyl sulfosuccinate and alkali salts of mono-chain alkylethoxy sulfosuccinate. Examples of nonionic surfactants that can be used in the coloring composition according to the present disclosure include alkyl polyglycosides, sorbitan esters, and acetylene glycols. Preferred examples of cationic surfactants that can be used in the coloring composition according to the present disclosure include quaternary ammonium compounds, and more preferred examples include quaternary ammonium compounds having a long-chain alkyl group (for example, an alkyl group having 10 or more carbon atoms, preferably an alkyl group having 10 to 24 carbon atoms). Examples include cetyltrimethylammonium chloride, dimethylstearylammonium chloride, trimethylacetylammonium bromide, stearyltrimethylammonium chloride, dimethylstearylbenzylammonium chloride, benzyltetradecyldimethylammonium chloride, dimethyldi-hydrogenated-tallow ammonium chloride, lauryldimethylbenzylammonium chloride, behenyltrimethylammonium chloride, lauryltrimethylammonium chloride, tris(oligooxy-ethyl)alkylammonium phosphate, and cetylpyridinium chloride. Amphoteric or zwitterionic surfactants that can be used in the coloring compositions according to the present disclosure include betaines such as fatty acid-amidoalkyl betaines and sulfobetaines (for example, laurylhydroxysulfobetaine).

[0116] When the coloring composition according to the present disclosure is used as an aqueous coloring composition, the coloring composition according to the present disclosure preferably contains an aqueous solvent. Examples of aqueous solvents include water, organic solvents that are soluble in water (preferably soluble at 25° C.), and mixed solvents thereof. Usable aqueous solvents include water, methanol, ethanol, isopropanol, n-propanol, butanol, n-pentanol, propylene glycol, ethylene glycol monoethyl ether, 1,2-hexanediol, butoxyethanol, phenoxyethanol, benzyl alcohol, propylene carbonate, and mixtures thereof. Among these, 1,2- or 1,3-propanediol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1,3- or 1,4-butanediol, diethylene glycol, diethylene glycol monomethyl or monoethyl ether, dipropylene glycol, or dipropylene glycol monomethyl or monoethyl ether are preferred. When the coloring composition according to the present disclosure is used as an aqueous coloring composition, the content of the compound represented by Formula 1, its tautomer, and a salt thereof is preferably 0.001% by mass to 30% by mass, more preferably 0.001% by mass to 20% by mass, even more preferably 0.1% by mass to 10% by mass, and particularly preferably 0.5% by mass to 10% by mass, relative to the total mass of the coloring composition. In addition, the aqueous solvent may be a combination of monohydric alcohols such as methanol, ethanol, isopropanol, and n-propanol; polyhydric alcohols such as glycerin and hexanetriol; ethyl carbitol; benzyl alcohol; benzyloxyethanol; propylene carbonate (4-methyl-1,3-dioxane-2-one); n-alkylpyrrolidone; and urea.

[0117] The coloring composition according to the present disclosure may include a thickener. Thickeners include oleic acid, cetyl alcohol, oleyl alcohol, sodium chloride, cetearyl alcohol, stearyl alcohol, and the like. The content of the thickener is preferably 0.05% by mass to 20% by mass, more preferably 0.1% by mass to 10% by mass, and particularly preferably 0.5% by mass to 5% by mass, relative to the total mass of the colored composition.

[0118] The coloring composition according to the present disclosure may contain coloring compounds (pigments, dyes, etc.) other than the compound represented by formula 1, its tautomers, and salts thereof. Any yellow dye can be used, including aryl or heteryl azo dyes, azomethine dyes, methine dyes, and quinone dyes, as well as quinophthalone dyes, nitro / nitroso dyes, acridine dyes, and acridinone dyes. Any magenta dye can be used, including, for example, aryl or heteryl azo dyes, azomethine dyes, methine dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, and xanthene dyes, quinone dyes such as naphthoquinone, anthraquinone, and anthrapyridone, and condensed polycyclic dyes such as dioxazine dyes. Any cyan dye can be used, including aryl or heteryl azo dyes, azomethine dyes, polymethine dyes such as cyanine dyes, oxonol dyes, and merocyanine dyes, carbonium dyes such as diphenylmethane dyes, triphenylmethane dyes, and xanthene dyes, phthalocyanine dyes, anthraquinone dyes, and indigo and thioindigo dyes. The ink may also contain a black dye. Examples of the black dye that can be used include disazo, trisazo, and tetraazo dyes, as well as dispersions of carbon black.

[0119] Furthermore, the coloring composition according to the present disclosure may contain a binder polymer, a polymerizable compound, a polymerization initiator, etc. As the binder polymer, the polymerizable compound, and the polymerization initiator, known ones can be used.

[0120] Other additives that can be used in the colored composition according to the present disclosure include silicone oils, hydrocarbon oils, polyolefins, fatty acid esters, and the like. The colored composition of the present disclosure may further contain other additives as needed, as long as the effects of the present disclosure are not impaired. Examples of additives for each application will be described later.

[0121] <Color toner> When the coloring composition according to the present disclosure is used for color toner applications, the content of the compound represented by Formula 1, its tautomer, and a salt thereof in the coloring composition for color toner is preferably 0.1 parts by mass or more, more preferably 1 to 20 parts by mass, and particularly preferably 2 to 10 parts by mass, based on 100 parts by mass of the coloring composition for color toner.

[0122] When the coloring composition according to the present disclosure is used for color toner applications, the coloring composition for color toner preferably contains a binder resin. As the binder resin, any binder that is generally used can be used, such as a styrene-based resin, an acrylic-based resin, a styrene / acrylic-based resin, or a polyester resin.

[0123] When the coloring composition according to the present disclosure is used for color toner applications, inorganic particles and / or organic particles can be externally added for the purpose of improving the fluidity, charge control, etc. of the coloring composition for color toner. For example, silica particles or titania particles whose surfaces have been treated with an alkyl group-containing coupling agent or the like are preferred. These particles preferably have a number average primary particle diameter of 10 nm to 500 nm, and are preferably added to the toner in an amount of 0.1% by mass to 20% by mass.

[0124] When the coloring composition according to the present disclosure is used for color toner applications, the coloring composition for color toner preferably contains a release agent. As the release agent, any of the conventionally used release agents can be used, specifically, polyolefins such as low molecular weight polypropylene, low molecular weight polyethylene, and ethylene-propylene copolymers, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax can be used. The content of the release agent is preferably 1% by mass to 5% by mass relative to the total mass of the color toner composition.

[0125] When the coloring composition according to the present disclosure is used for color toner applications, the coloring composition for color toner preferably contains a charge control agent. Examples of the charge control agent include quaternary ammonium salt compounds and calixarene compounds.

[0126] When the coloring composition according to the present disclosure is used for color toner applications, the coloring composition for color toner may contain a carrier. The carrier may be either an uncoated carrier consisting of only magnetic material particles such as iron or ferrite, or a resin-coated carrier in which the surfaces of magnetic material particles are coated with a resin or the like. The average particle size of the carrier is preferably 30 μm to 150 μm in terms of volume average particle size.

[0127] <Inkjet recording ink> When the coloring composition according to the present disclosure is used as an ink for inkjet recording, the ink for inkjet recording is preferably an ink obtained by dissolving and / or dispersing the coloring composition in an oleophilic medium or an aqueous medium, and more preferably an ink using an aqueous medium (preferably an aqueous solvent). When the coloring composition according to the present disclosure is used as an ink for inkjet recording, the ink for inkjet recording may contain, as necessary, known additives such as an anti-drying agent (humectant), an anti-fading agent, an emulsion stabilizer, a penetration enhancer, an ultraviolet absorber, an antiseptic, an anti-fungal agent, a pH adjuster, a surface hearing aid, an antifoaming agent, a viscosity adjuster, a dispersant, a dispersion stabilizer, an anti-rust agent, and a chelating agent. In the case of a water-soluble ink, these various additives are added directly to the ink liquid. In the case of an oil-soluble dye in the form of a dispersion, they are generally added to the dispersion after the dye dispersion is prepared, but they may also be added to the oil phase or water phase during preparation.

[0128] The anti-drying agent is suitably used for the purpose of preventing clogging due to drying of ink for ink-jet recording at the ink ejection openings of the nozzles used in the ink-jet recording method. As the drying inhibitor, a water-soluble organic solvent having a vapor pressure lower than that of water is preferred.Specific examples include polyhydric alcohols such as ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerin, and trimethylolpropane; lower alkyl ethers of polyhydric alcohols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, and triethylene glycol monoethyl (or butyl) ether; heterocyclic compounds such as 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and N-ethylmorpholine; sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, and 3-sulfolene; polyfunctional compounds such as diacetone alcohol and diethanolamine; and urea derivatives.Among these, polyhydric alcohols such as glycerin and diethylene glycol are more preferred. The above-mentioned drying inhibitors may be used alone or in combination of two or more. The content of these anti-drying agents in the inkjet recording ink is preferably 10% by mass to 50% by mass.

[0129] The ultraviolet absorber is used for the purpose of improving the storage stability of the image. Examples of ultraviolet absorbers include benzotriazole compounds described in JP-A Nos. 58-185677, 61-190537, 2-782, 5-197075, and 9-34057, benzophenone compounds described in JP-A Nos. 46-2784, 5-194483, and U.S. Pat. No. 3,214,463, and the like, and JP-B Nos. 48-30492, 56-21141, and 10-8810. Also usable are cinnamic acid compounds described in JP-A No. 6, etc.; triazine compounds described in JP-A Nos. 4-298503, 8-53427, 8-239368, 10-182621, and JP-T No. 8-501291, etc.; compounds that absorb ultraviolet light and emit fluorescence, such as compounds described in Research Disclosure No. 24239, and stilbene and benzoxazole compounds, which are so-called fluorescent brighteners.

[0130] The anti-fading agent is used for the purpose of improving the storage stability of the image. As the antifading agent, various organic and metal complex antifading agents can be used. Organic antifading agents include hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocycles, etc., and metal complexes include nickel complexes and zinc complexes. More specifically, compounds described in Sections I to J of Section VII of Research Disclosure No. 17643, No. 15162, No. 18716, page 650, left column, No. 36544, page 527, No. 307105, page 872, and No. 15162, as well as compounds included in the general formulas and compound examples of representative compounds described on pages 127 to 137 of JP-A-62-215272, can be used.

[0131] Examples of antifungal agents include sodium dehydroacetate, sodium benzoate, sodium pyridinethione-1-oxide, p-hydroxybenzoic acid ethyl ester, 1,2-benzisothiazolin-3-one and salts thereof, etc. These are preferably contained in an amount of 0.02% by mass to 1.00% by mass relative to the total mass of the ink.

[0132] The pH adjuster may be a neutralizing agent (organic base or inorganic alkali). The pH adjuster is added so that the inkjet recording ink has a pH of preferably 6 to 10, and more preferably 7 to 10, for the purpose of improving the storage stability of the inkjet recording ink.

[0133] Examples of surface tension adjusters include nonionic, cationic, and anionic surfactants. The surface tension of the inkjet recording ink is preferably 25 mN / m to 70 mN / m, and more preferably 25 mN / m to 60 mN / m, at 25°C. The viscosity of the inkjet recording ink is preferably 30 mPa·s or less at 25°C, and more preferably adjusted to 20 mPa·s or less. Examples of surfactants include anionic surfactants such as fatty acid salts, alkyl sulfate salts, alkylbenzenesulfonates, alkylnaphthalenesulfonates, dialkylsulfosuccinates, alkyl phosphate salts, naphthalenesulfonate-formaldehyde condensates, and polyoxyethylene alkyl sulfate salts, as well as nonionic surfactants such as polyoxyethylene alkyl ethers, polyoxyethylene alkyl allyl ethers, polyoxyethylene fatty acid esters, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters, polyoxyethylene alkylamines, glycerin fatty acid esters, and oxyethyleneoxypropylene block copolymers. Also preferred are SURFYNOLS (Air Products & Chemicals), an acetylene-based polyoxyethylene oxide surfactant. Also preferred are amine oxide amphoteric surfactants such as N,N-dimethyl-N-alkylamine oxide. Furthermore, surfactants listed on pages (37) to (38) of JP-A-59-157636 and Research Disclosure No. 308119 (1989) can also be used. As the defoaming agent, fluorine-based compounds, silicone-based compounds, chelating agents such as ethylenediaminetetraacetic acid (EDTA), and the like can also be used as needed.

[0134] When dispersing the compound represented by Formula 1, its tautomers, and salts thereof in an aqueous medium, it is preferable to disperse colored microparticles containing the compound and an oil-soluble polymer in an aqueous medium, as described in JP-A Nos. 11-286637, 2001-240763, 2001-262039, and 2001-247788, or to disperse the compound represented by Formula 1, its tautomers, and salts thereof dissolved in a high-boiling organic solvent in an aqueous medium, as described in JP-A Nos. 2001-262018, 2001-240763, 2001-335734, and 2002-80772. The specific methods, oil-soluble polymers, high-boiling organic solvents, additives, and amounts thereof used for dispersing the compound represented by Formula 1, its tautomers, and salts thereof in an aqueous medium are preferably those described in the above patent publications. Alternatively, the compound represented by Formula 1, its tautomer, and a salt thereof may be dispersed in a fine particle state as a solid. A dispersant or surfactant may be used during dispersion. Dispersion equipment that can be used includes a simple stirrer or impeller stirring method, an in-line stirring method, a mill method (e.g., a colloid mill, a ball mill, a sand mill, an attritor, a roll mill, an agitator mill, etc.), an ultrasonic method, and a high-pressure emulsification dispersion method (a high-pressure homogenizer; specific commercially available equipment includes a Gaulin homogenizer, a Microfluidizer, and a DeBEE2000). In addition to the above-mentioned patents, methods for preparing the inkjet recording inks are described in detail in JP-A Nos. 5-148436, 5-295312, 7-97541, 7-82515, 7-118584, 11-286637, and 2001-271003, and these methods can be used to prepare inkjet recording inks containing the coloring compositions according to the present disclosure.

[0135] The aqueous medium is a mixture containing water as the main component and, if desired, containing a water-miscible organic solvent. Examples of the water-miscible organic solvent include alcohols (e.g., methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, and benzyl alcohol), polyhydric alcohols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, and thiodiglycol), glycol derivatives (e.g., ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, and dipropylene glycol monomethyl ether), and Examples of suitable water-miscible organic solvents include ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, and tetramethylpropylenediamine, as well as other polar solvents such as formamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, and acetone. The water-miscible organic solvents may be used in combination of two or more.

[0136] When the coloring composition according to the present disclosure is used as an ink for inkjet recording, the compound represented by Formula 1, its tautomer, or a salt thereof is preferably contained in an amount of 0.2 parts by mass to 10 parts by mass, and more preferably 1 part by mass to 6 parts by mass, per 100 parts by mass of the ink for inkjet recording. The inkjet recording ink may also contain other dyes. When two or more dyes are used in combination, it is preferable that the total content of the dyes is within the above-mentioned range.

[0137] (Dyeing method and dyed products) The dyeing method according to the present disclosure is a dyeing method using a compound represented by formula 1, a tautomer thereof, or a salt thereof, and is preferably a dyeing method using a coloring composition according to the present disclosure. The dyed article according to the present disclosure comprises a compound represented by formula 1, a tautomer thereof, or a salt thereof.

[0138] The dyeing method using the compound represented by formula 1, its tautomer, or a salt thereof may be any method that uses at least one selected from the group consisting of the compound represented by formula 1, its tautomer, and a salt thereof as a dye, and can be, for example, a method such as immersion, kneading, coating, printing, or inkjet printing. Furthermore, the dyeing method according to the present disclosure can use any known dyeing method, except that the compound represented by formula 1, its tautomer, or a salt thereof is used.

[0139] The dyed article according to the present disclosure may contain a pigment and / or dye other than the compound represented by formula 1, its tautomer, or a salt thereof. Furthermore, the dyed portion containing the compound represented by formula 1, its tautomer, or a salt thereof in the dyed article according to the present disclosure may be a part of the dyed article or the whole of the dyed article. As the substrate for the dyeing of the present disclosure, natural fibers such as silk, cotton, and linen; synthetic fibers such as nylon, polyester, acrylic, and polyurethane; inorganic materials such as glass, metal, and ceramic; and paper such as plain paper, resin-coated paper, and inkjet recording paper can be used. [Example]

[0140] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited thereto. In these examples, "%" and "parts" mean "% by mass" and "parts by mass," respectively, unless otherwise specified.

[0141] Example 1: Synthesis of Exemplary Compound M-2 and Exemplary Compound D-2

[0142] [ka]

[0143] A mixture of 4.4 g of 5-amino-3-methylthio-1,2,4-thiadiazole, 8.8 g of concentrated sulfuric acid, 4.2 g of water, and 20 mL of acetic acid was stirred under ice cooling. To this mixture, a solution of 2.3 g of sodium nitrite and 4 mL of water was added dropwise, and after stirring for 1 hour, 4.9 mL of acetic acid was added to obtain a diazonium salt solution. Separately, a mixture of 6.6 g of resorcinol (1,3-dihydroxybenzene) and 60 mL of methanol (MeOH) was prepared, and the above diazonium salt solution was added dropwise under ice cooling and allowed to stand for 4 days. 60 mL of water was added to the reaction mixture, and the precipitated crystals were collected by filtration and washed with water and methanol. The obtained crystals were dried to obtain 6.6 g of exemplary compound M-2. 1 H-NMR(DMSO-d6) δ = 11.6 (br., 1H), 7.71 (d, 1H), 6.51 (dd, 1H), 6.46 (d, 1H), 2.67 (s, 3H)

[0144] A mixture of 2.3 g of concentrated sulfuric acid, 13.8 g of acetic acid (AcOH), and 5.9 g of 5-amino-1-methylpyrazole phosphate was stirred under ice cooling, and 9.5 g of nitrosylsulfuric acid (43%) was added dropwise. After stirring for 20 minutes, the diazonium salt obtained above was added dropwise to a mixture of 5.9 g of exemplary compound M-2, 6.5 g of sodium acetate (AcONa), and 60 mL of methanol under ice cooling. After stirring at room temperature (20°C to 25°C, the same applies below) for 1 hour, the precipitated crystals were collected by filtration and washed with water and methanol. The obtained crystals were stirred in 50 mL of acetonitrile, collected by filtration, washed with acetonitrile, and dried to obtain 4.5 g of exemplary compound D-2. 1 H-NMR(CDCl3) δ = 15.0 (br., 1H), 7.51 (d, 1H), 7.31 (d, 1H), 6.56 (d, 1H), 6.53 (d, 1H), 4.06 (s, 3H), 2.67 (s, 3H) Maximum absorption wavelength (λmax): 492 nm, molar absorption coefficient ε: 2.63 × 10 4 (N,N-dimethylformamide (DMF))

[0145] <Evaluation 1: Dyeing of inkjet paper with exemplary compound D-2> A surfactant solution was prepared by adding 62 mg of Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.) to 100 mL of pure water. 2.5 g of the surfactant solution was added to a mixture of 50 mg of exemplary compound D-2 and 2.5 mL of 0.1 M (M = mol / L) aqueous sodium hydroxide solution, and the mixture was uniformly dissolved. This resulted in a colored composition containing a salt of exemplary compound D-2, which is a compound according to the present disclosure. The obtained coloring composition was applied to inkjet paper "Gasai" (manufactured by Fujifilm Corporation) using a bar coater. A brown dyed product was obtained. * , a * and b * was measured using i1 Pro (manufactured by X-Rite). The results are shown in Table 1 below.

[0146] (Comparative Example 1: Dyeing of inkjet paper with Acid Brown M) A colored composition containing a salt of the comparative compound Acid Brown M was obtained in the same manner as above, except that Acid Brown M was used instead of the above exemplary compound D-2.

[0147] [ka]

[0148] The obtained coloring composition was applied to inkjet paper, GASAI (registered trademark, manufactured by FUJIFILM Corporation) using a bar coater. A reddish brown dyed product was obtained. * , a * and b * was measured using i1 Pro (manufactured by X-Rite). The results are shown in Table 1 below.

[0149] [Table 1]

[0150] The column for compound in Table 1 indicates the exemplary compounds subjected to the staining evaluation.

[0151] Exemplary compound D-2, which is a compound according to the present disclosure, had a hue with lower saturation and lightness than comparative compound Acid Brown M.

[0152] Example 2: Synthesis of Exemplary Compound M-11 and Exemplary Compound D-11

[0153] [ka]

[0154] In a 200 mL three-neck flask, 14.7 g of 5-amino-3-methylthio-1,2,4-thiadiazole was dissolved in 80 mL of phosphoric acid (85%, Fujifilm Wako Pure Chemical Industries, Ltd.), and the internal temperature was cooled to 0°C. To this, 6.9 g of sodium nitrite (Fujifilm Wako Pure Chemical Industries, Ltd.) was slowly added in portions while maintaining the internal temperature below 5°C. After the addition was complete, the mixture was stirred at an internal temperature of 0 to 5°C for 1 hour to prepare a diazonium salt solution. In a separate 500 mL three-neck flask, 12.6 g of 1,3,5-benzenetriol (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.) was dissolved in 200 mL of methanol and cooled to an internal temperature of 5°C. The previously prepared diazonium salt solution was slowly added to the flask while maintaining the internal temperature at 10°C or below. After the addition was complete, the mixture was stirred at an internal temperature of 0-5°C for 30 minutes, and then at 25°C for 1 hour. The precipitated crystals were collected by filtration, washed three times with 200 mL of methanol, and then dried in a 50°C air dryer for 6 hours to obtain powder crystals of exemplary compound M-11. Yield: 25.6 g (90%) 1 H-NMR(DMSO-d6) δ = 12.71 (br., 2H), 5.96 (s, 2H), 2.64 (s, 3H)

[0155] In a 200 mL three-neck flask, 9.8 g of 5-amino-1-methylpyrazole phosphate was dissolved in 80 mL of phosphoric acid (85%, Fujifilm Wako Pure Chemical Industries, Ltd.), and the internal temperature was cooled to 0°C. 3.5 g of sodium nitrite (Fujifilm Wako Pure Chemical Industries, Ltd.) was slowly added in portions while maintaining the internal temperature below 5°C. After the addition was complete, the mixture was stirred at an internal temperature of 0 to 5°C for 1 hour to prepare a diazonium salt solution. In a separate 500 mL three-neck flask, 14.2 g of exemplary compound M-11 was suspended and dispersed in 200 mL of methanol, and the internal temperature was cooled to 5°C. The diazonium salt solution prepared earlier was slowly added to the suspension while maintaining the internal temperature at 10°C or below. After the addition was complete, the mixture was stirred at an internal temperature of 0°C to 5°C for 30 minutes, and then stirred at 25°C for 1 hour. The precipitated crystals were collected by filtration and washed three times with 200 mL of methanol. The crystals were heated, suspended, and washed in 100 mL of acetonitrile at 50°C, and then dried in a 50°C air dryer for 6 hours, yielding green glossy crystals of exemplary compound D-11. Yield: 16.2 g (83%) 1 H-NMR(DMSO-d6) δ = 10.2 (br., 2H), 7.31 (d, 1H), , 6.66 (d, 1H), 6.40-6.59(br,1H),5.79 (s, 1H), 4.10 (s, 3H), 2.56 (s, 3H) λmax: 424 nm, ε: 2.44 × 10 4 (DMF)

[0156] The hue of the example compound D-11 was low in saturation and brightness.

[0157] Example 3: Synthesis of exemplary compound N-100

[0158] [ka]

[0159] A mixture of 3.5 g of concentrated sulfuric acid, 20.7 g of acetic acid (AcOH), and 8.9 g of 5-amino-1-methylpyrazole phosphate was stirred under ice cooling, and 14.3 g of nitrosylsulfuric acid (43%) was added dropwise to obtain a diazonium salt solution. After stirring for 30 minutes, the diazonium salt solution obtained above was added dropwise to a mixture of 6.3 g of 3-hydroxy-N,N-dimethylaniline and 125 mL of methanol under ice cooling. After stirring for 1 hour at room temperature (20°C to 25°C, the same applies below), 5% aqueous sodium bicarbonate solution was added under ice cooling until the pH reached 7. The precipitated crystals were collected by filtration and washed with water. The obtained crystals were dried to obtain 9.8 g of exemplary compound N-100. 1 H-NMR(CDCl3)δ = 7.7 (d, 1H), 7.5 (s, 1H), 6.5 (d, 2H), 6.2 (s, 2H), 4.0 (s, 3H), 3.1 (s, 6H). Spectroscopic characteristics in N,N-dimethylformamide: λmax: 470 nm, molar absorption coefficient ε: 4.00 × 10 4 .

[0160] 3-Hydroxy-N,N-dimethylaniline has three reaction sites where this reaction can occur in a diazo coupling reaction, but exemplary compound N-100 can be selectively obtained. As shown below, exemplary compound N-100 functions as a valuable synthetic intermediate for obtaining exemplary compounds N-1, N-2, and N-6.

[0161] Example 4: Synthesis of exemplary compound N-1

[0162] [ka]

[0163] A mixture of 1.2 g of concentrated sulfuric acid, 6.9 g of acetic acid (AcOH), and 3 g of 5-amino-1-methylpyrazole phosphate was stirred under ice cooling, and 4.8 g of nitrosylsulfuric acid (43%) was added dropwise to obtain a diazonium salt solution. After stirring for 30 minutes, the diazonium salt solution obtained above was added dropwise to a mixture of 3.1 g of Intermediate A and 60 mL of methanol under ice cooling. After stirring at room temperature (20°C to 25°C, the same applies below), 5% aqueous sodium bicarbonate solution was added under ice cooling until the pH reached 7. The precipitated crystals were collected by filtration and washed with water. The obtained crystals were dried and purified by silica gel chromatography to obtain 2.0 g of Exemplified Compound N-1. 1 H-NMR(CDCl3)δ = 12.7 (s, 1H), 8.2 (s, 1H), 7.5 (d, 2H), 6.56 (d, 2H), 6.35 (s, 1H), 4.3 (s, 3H), 4.1(s, 3h),3.3 (s, 6H). Spectroscopic characteristics in N,N-dimethylformamide: λmax: 521 nm, molar absorption coefficient ε: 2.03 × 10 4 , λmax2: 442 nm, molar extinction coefficient ε: 2.13 × 10 4 , λmax3: 347 nm, molar extinction coefficient ε: 2.13 × 10 4 .

[0164] Example 5: Synthesis of Exemplary Compound N-2 and Exemplary Compound N-6

[0165] [ka]

[0166] A mixture of 3.0 g of concentrated sulfuric acid, 17.3 g of acetic acid (AcOH), and 7.5 g of 5-amino-1-methylpyrazole phosphate was stirred under ice cooling, and 12.0 g of nitrosylsulfuric acid (43%) was added dropwise to obtain a diazonium salt solution. After 30 minutes of stirring, the diazonium salt solution obtained above was added dropwise to a mixture of 3.1 g of exemplary compound N-100 and 60 mL of methanol under ice cooling. After stirring at room temperature (20°C to 25°C, the same applies below), 5% aqueous sodium bicarbonate solution was added under ice cooling until the pH reached 7. The precipitated crystals were collected by filtration and washed with water. The obtained crystals were dried and purified by silica gel chromatography to obtain 2.5 g of exemplary compound N-2 and 1.0 g of exemplary compound N-6.

[0167] ( 1 H-NMR (CDCl3) Exemplary compound N-2: δ = 14.9 (s, 1H), 8.6 (s, 1H), 7.6 (d, 3H), 6.56 (d, 2H), 6.35 (s, 1H), 4.3 (s, 3H), 4.2 (s, 3H), 4.1 (s, 3H), 3.5 (s, 6H) Exemplary compound N-6: δ = 14.7 (s, 1H), 7.9 (d, 1H), 7.5 (d, 2H), 6.6 (d, 2H), 6.4 (d, 2H), 4.2 (s, 3H), 4.1 (s, 3H),3.4 (s, 6H)

[0168] (Spectroscopic properties in N,N-dimethylformamide) Exemplary compound N1: λmax1: 521 nm, molar extinction coefficient ε: 2.03 × 10 4 λmax2: 442 nm, molar extinction coefficient ε: 2.13 × 10 4 λmax3: 347 nm, molar absorption coefficient ε: 2.13 × 10 4 Exemplary compound N-2: λmax1: 600 nm, molar absorption coefficient ε: 1.70 × 10 4 λmax2: 496 nm, molar absorption coefficient ε: 2.13 × 10 4 λmax3: 419 nm, molar extinction coefficient ε: 2.70 × 10 4 Exemplary compound N-6: λmax1: 449 nm, molar extinction coefficient ε: 3.45 × 10 4 λmax2: 420 nm, molar extinction coefficient ε: 3.35 × 10 4

[0169] <Evaluation 2: Dyeing of inkjet paper with exemplary compounds N-1, N-2, or N-6> (1) Preparation of Coloring Composition Containing Salt of Exemplary Compound N-1> A surfactant solution was prepared by adding 62 mg of Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.) to 100 mL of pure water. 2.5 g of the surfactant solution was added to a mixture of 47 mg of exemplary compound N-1 and 2.5 mL of 0.1 M (M = mol / L) aqueous sodium hydroxide solution, and the mixture was uniformly dissolved. This resulted in a colored composition containing a salt of exemplary compound N-1, which is a compound according to the present disclosure.

[0170] (2) Preparation of a coloring composition containing a salt of exemplary compound N-2 A colored composition containing a salt of exemplary compound N-2, which is a compound according to the present disclosure, was obtained in the same manner as above, except that 61 mg of exemplary compound N-2 was used instead of exemplary compound N-1.

[0171] (3) Preparation of Coloring Composition Containing Salt of Exemplary Compound N-6> A colored composition containing a salt of exemplary compound N-6, which is a compound according to the present disclosure, was obtained in the same manner as above, except that 47 mg of exemplary compound N-6 was used instead of exemplary compound N-1.

[0172] Each of the coloring compositions obtained above was applied to inkjet paper "Gasai" (manufactured by Fujifilm Corporation) using a bar coater. A brown dyed product was obtained. * , a * and b * was measured using i1 Pro (manufactured by X-Rite).

[0173] The above evaluation results are shown in the following Table 2. Table 2 also shows the evaluation results of Comparative Example 1.

[0174] [Table 2]

[0175] The column for compounds in Table 2 shows the exemplary compounds used in the evaluation of the colored compositions.

[0176] Exemplary compounds N-1, N-2, and N-6, which are compounds according to the present disclosure, had hues with lower saturation and brightness than the comparative compound Acid Brown M.

[0177] The disclosures of Japanese Patent Application No. 2020-173290, filed on October 14, 2020, and Japanese Patent Application No. 2020-217653, filed on December 25, 2020, are incorporated herein by reference in their entirety. All documents, patent applications, and technical standards mentioned herein are incorporated herein by reference to the same extent as if each individual document, patent application, and technical standard was specifically and individually indicated to be incorporated by reference.

Claims

1. A compound represented by the following formula 1, a tautomer thereof, or a salt thereof: 【Chemistry 1】 In Formula 1, X- represents R １ O-, R ２ａ R ２ｂ N- or R ３ represents S-, and R １ , R ２ａ and R ２ｂ each independently represents a hydrogen atom or an alkyl group; R ３ represents an alkyl group, and X- is R ２ａ R ２ｂ If N-, R ２ａ and R ２ｂ may be the same or different, R ２ａ and R ２ｂ may bond to form a nitrogen-containing heterocycle, each R independently represents a halogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, a carboxy group, a carbamoyl group, a cyano group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfo group, n represents 0, 1, 2, or 3, and when n represents 2 or 3, R may be the same or different, Ar represents an aromatic hydrocarbon group or a heterocyclic group, m1 represents 2 or 3, and Ar may be the same or different, with the proviso that at least one Ar is a group represented by any of the following formulas (A-1) to (A-7), (A-9) to (A-25), (A-27), and (A-28). 【Chemistry 2】 【Transformation 3】 【Chemistry 4】 In formulas (A-1) to (A-7), (A-9) to (A-25), (A-27) and (A-28), * represents the position at which the azo group in formula (1) is bonded, and R ２１ ~R ２７ , R ３１ and R ３３ to R 50 , R 52 and R ５３ each independently represents a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclicthio group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group; R ２８ and R ３２ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclicthio group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group; R ２１ to R 28 , R 31 to R 50 , R 52 and R ５３ adjacent groups among these may bond to each other to form a saturated or unsaturated 5- or 6-membered ring structure, a, p, q, r, and s represent integers of 0 to 4, b and c represent integers of 0 to 6, d, e, f, g, t, and u represent integers of 0 to 3, h, i, j, k, l, and o represent integers of 0 to 2, m represents 0 or 1, and R ２１ ~R ２８ , R ３１ ~R ５０ , R ５２ and R ５３ The two or more groups represented by the formula (I) may be the same or different from each other.

2. The compound according to claim 1, wherein m1 is 2, or a tautomer or salt thereof.

3. 3. The compound, its tautomer, or a salt thereof according to claim 1 or 2, wherein X- is bonded to the meta position relative to the hydroxy group.

4. A coloring composition comprising the compound according to any one of claims 1 to 3, a tautomer thereof, or a salt thereof.

5. The coloring composition according to claim 4, further comprising an aqueous solvent.

6. A dyeing method using the coloring composition according to claim 4 or 5.

7. A dyed article comprising the compound according to any one of claims 1 to 3, its tautomer, or a salt thereof.

8. A method for producing the compound according to any one of claims 1 to 3, its tautomer, or a salt thereof, comprising the steps of: reacting a diazonium salt represented by the following formula 5 with a compound represented by the following formula 6 to obtain a compound represented by the following formula 7; and reacting the obtained compound represented by the formula 7 with a diazonium salt represented by the following formula 8. 【Transformation 5】 In formulas 5 to 8, Ar １ and Ar ２ each independently represents an aromatic hydrocarbon group or a heterocyclic group; Ar １ and Ar ２ at least one of the following is a group represented by any one of the following formulas (A-1) to (A-7), (A-9) to (A-25), (A-27) and (A-28): R each independently represents a halogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, a carboxy group, a carbamoyl group, a cyano group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfo group; X- is R １ O-, R ２ａ R ２ｂ N- or R ３ represents S-, and R １ , R ２ａ and R ２ｂ each independently represents a hydrogen atom or an alkyl group; R ３ represents an alkyl group, n represents 0, 1, 2 or 3, and when n represents 2 or 3, R may be the same or different. １ and Ar ２ and cannot simultaneously be an aromatic hydrocarbon group. 【Transformation 6】 【Transformation 7】 【Transformation 8】 In formulas (A-1) to (A-7), (A-9) to (A-25), (A-27) and (A-28), * represents the position at which the azo group in formula (1) is bonded, and R ２１ ~R ２７ , R ３１ and R ３３ to R 50 , R 52 and R ５３ each independently represents a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclicthio group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group; R ２８ and R ３２ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclicthio group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group; R ２１ to R 28 , R 31 to R 50 , R 52 and R ５３ adjacent groups among these may bond to each other to form a saturated or unsaturated 5- or 6-membered ring structure, a, p, q, r, and s represent integers of 0 to 4, b and c represent integers of 0 to 6, d, e, f, g, t, and u represent integers of 0 to 3, h, i, j, k, l, and o represent integers of 0 to 2, m represents 0 or 1, and R ２１ ~R ２８ , R ３１ ~R ５０ , R ５２ and R ５３ The two or more groups represented by the formula (I) may be the same or different from each other.

9. A method for producing the compound according to any one of claims 1 to 3, its tautomer, or a salt thereof, comprising the steps of: reacting a diazonium salt represented by the following formula 5 with a compound represented by the following formula 10 to obtain a compound represented by the following formula 11; and reacting the obtained compound represented by the formula 11 with a diazonium salt represented by the following formula 8 to obtain a compound represented by the following formula 12. 【Chemistry 9】 In Formula 5, Formula 8, and Formulas 10 to 12, Ar １ and Ar ２ each independently represents an aromatic hydrocarbon group or a heterocyclic group; Ar １ and Ar ２ is a group represented by any one of the following formulas (A-1) to (A-7), (A-9) to (A-25), (A-27) and (A-28), and R each independently represents a halogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, a carboxy group, a carbamoyl group, a cyano group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group or a sulfo group, and n1 represents 0, 1 or 2, and when n1 represents 2, R may be the same or different. １ and Ar ２ and cannot simultaneously be an aromatic hydrocarbon group. 【Chemistry 10】 【Chemistry 11】 【Chemistry 12】 In formulas (A-1) to (A-7), (A-9) to (A-25), (A-27) and (A-28), * represents the position at which the azo group in formula (1) is bonded, and R ２１ ~R ２７ , R ３１ and R ３３ to R 50 , R 52 and R ５３ each independently represents a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclicthio group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group; R ２８ and R ３２ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclicthio group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group; R ２１ to R 28 , R 31 to R 50 , R 52 and R ５３ adjacent groups among these may bond to each other to form a saturated or unsaturated 5- or 6-membered ring structure, a, p, q, r, and s represent integers of 0 to 4, b and c represent integers of 0 to 6, d, e, f, g, t, and u represent integers of 0 to 3, h, i, j, k, l, and o represent integers of 0 to 2, m represents 0 or 1, and R ２１ ~R ２８ , R ３１ ~R ５０ , R ５２ and R ５３ The two or more groups represented by the formula (I) may be the same or different from each other.

10. A method for producing the compound according to any one of claims 1 to 3, its tautomer, or a salt thereof, comprising the steps of: reacting a diazonium salt represented by the following formula 5 with a compound represented by the following formula 13 to obtain a compound represented by the following formula 14; and reacting the obtained compound represented by the formula 14 with a diazonium salt represented by the following formula 8 to obtain a compound represented by the following formula 15. 【Chemistry 13】 In Formula 5, Formula 8 and Formula 13 to Formula 15, Ar １ and Ar ２ each independently represents an aromatic hydrocarbon group or a heterocyclic group; Ar １ and Ar ２ At least one of R is a group represented by any one of the following formulas (A-1) to (A-7), (A-9) to (A-25), (A-27) and (A-28). ２ａ and R ２ｂ each independently represents a hydrogen atom or an alkyl group; R ２ａ and R ２ｂ may be the same or different, R ２ａ and R ２ｂ may bond to form a nitrogen-containing heterocycle. Each R independently represents a halogen atom, a hydroxy group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, a carboxy group, a carbamoyl group, a cyano group, an acylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, an alkylsulfonyl group, an arylsulfonyl group, or a sulfo group, and n1 represents 0, 1, or 2, and when n1 represents 2, R may be the same or different. However, Ar １ and Ar ２ and cannot simultaneously be an aromatic hydrocarbon group. 【Chemistry 14】 【Chemistry 15】 【Chemistry 16】 In formulas (A-1) to (A-7), (A-9) to (A-25), (A-27) and (A-28), * represents the position at which the azo group in formula (1) is bonded, and R ２１ ~R ２７ , R ３１ and R ３３ to R 50 , R 52 and R ５３ each independently represents a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclicthio group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group; R ２８ and R ３２ each independently represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxy group, a nitro group, an alkoxy group, an aryloxy group, an amino group, an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclicthio group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group, or a carbamoyl group; R ２１ to R 28 , R 31 to R 50 , R 52 and R ５３ adjacent groups among these may bond to each other to form a saturated or unsaturated 5- or 6-membered ring structure, a, p, q, r, and s represent integers of 0 to 4, b and c represent integers of 0 to 6, d, e, f, g, t, and u represent integers of 0 to 3, h, i, j, k, l, and o represent integers of 0 to 2, m represents 0 or 1, and R ２１ ~R ２８ , R ３１ ~R ５０ , R ５２ and R ５３ The two or more groups represented by the formula (I) may be the same or different from each other.

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