Compound, its tautomer or salt thereof, method for producing the same, coloring composition, dyeing method and dyed product

Abstract

The present invention provides a compound represented by Formula 1, a tautomer thereof, or a salt thereof, and a method for producing the same, a coloring composition and a dyed product containing the compound represented by Formula 1, a tautomer thereof, or a salt thereof, and a dyeing method using the compound represented by Formula 1, a tautomer thereof, or a salt thereof. The definitions of X, R, Ar, n, and m1 in Formula 1 are shown in the specification.

Description

Technical Field

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

[0002] In the past, azo dyes have been used as dyes in various fields because they have various visible light absorption properties, such as coloring of synthetic resins, printing inks, dyes for sublimation-type thermal transfer materials, inkjet inks, and dyes for color filters.

[0003] In recent years, color images have become the mainstream as image recording materials, and the use of pigments has also become diversified. Specifically, it is widely used in recording materials for inkjet methods, recording materials for thermal transfer methods, recording materials for electronic photography methods, transfer-type silver halide photosensitive materials, printing inks, etc. In addition, in imaging elements such as charge coupled devices (CCDs) and complementary metal oxide semiconductors (CMOS) in photographic equipment, and in liquid crystal displays (LCDs) and plasma display panels (PDPs) in displays, color filters for recording and reproducing color images are used. In these color image recording materials or color filters, in order to reproduce or record full-color images, colorants (dyes or pigments) of the three primary colors of the so-called additive color mixing method or subtractive color mixing method are used.

[0004] Furthermore, various dyes for dyeing fibers and the like have long been known, and in recent years, many hair dyes for dyeing hair such as hair have been developed.

[0005] Hair dyes can be classified according to whether they have a decolorizing effect on the dye or melanin used. Representative examples of hair dyes include two-component permanent hair dyes composed of a first component containing an alkali agent, an oxidation dye, or a direct dye such as a nitro dye, and a second component containing an oxidizing agent, and a one-component semi-permanent hair dye containing an organic acid or an alkali agent and at least one of an acid dye, a basic dye, a nitro dye, or the like.

[0006] Examples of conventional azo dyes include azo dyes described in JP-A No. 2017-515930. Summary of the invention

[0007] Technical issues to be solved by the invention

[0008] However, sometimes a pigment with a special hue other than the existing yellow, magenta, and cyan is needed. For example, a pigment with low chroma or a pigment with an absorption waveform having a wide absorption in the entire visible light region is needed. Therefore, the current situation is that there is no strong colorant that has these preferred absorption characteristics and can withstand various usage conditions and environmental conditions, and improvement is strongly desired.

[0009] The problem to be solved by the embodiments of the present invention is to provide a novel compound, its tautomer or a salt thereof.

[0010] A problem to be solved by another embodiment of the present invention is to provide a coloring composition having a hue with low chroma.

[0011] Another embodiment of the present invention aims to provide a method for producing the above-mentioned compound, its tautomer or its salt, and a dyeing method and a dyed product using the above-mentioned compound, its tautomer or its salt.

[0012] Means for solving technical problems

[0013] Means for solving the above-mentioned problems include the following aspects.

[0014] <1> A compound represented by the following formula 1, its tautomer or a salt thereof.

[0015] [Chemical formula 1]

[0016]

[0017] In formula 1, X- represents R 1 O-、R 2a R 2b N- or R 3 S-, R 1 , R 2a and R 2b Each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group. 2a R 2b N-, R 2a and R 2b Can be the same or different, R 2a With R 2b can be bonded to form a nitrogen-containing heterocyclic ring. R independently represents a substituent, n represents 0, 1, 2 or 3, when n represents 2 or 3, R can be the same or different. Ar represents an aromatic hydrocarbon group or a heterocyclic group, m1 represents 1, 2 or 3, when m1 represents 2 or 3, Ar can be the same or different. Wherein, at least one of Ar is a heterocyclic group.

[0018] <2> according to <1> The compound, its tautomer or its salt, wherein m1 is 2 or 3.

[0019] <3> according to <2> The compound, its tautomer or its salt, wherein m1 is 2.

[0020] <4> according to <1> to <3> The compound, its tautomer or a salt thereof described in any one of the preceding claims, wherein the bonding position of X- is meta-position relative to the hydroxyl group.

[0021] <5> according to <1> to <4> The compound, its tautomer or its salt according to any one of the preceding claims, wherein R is a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, a carboxyl 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.

[0022] <6> according to <1> to <5> The compound, its tautomer or a salt thereof according to any one of the preceding claims, wherein at least one of Ar is a group represented by any of the following formulae (A-1) to (A-28).

[0023] [Chemical formula 2]

[0024]

[0025] [Chemical formula 3]

[0026]

[0027] [Chemical formula 4]

[0028]

[0029] In formulae (A-1) to (A-28), * indicates the position of bonding to the azo group in formula 1, 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 hydroxyl 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, and 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 hydroxyl 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, and R 21 ~R 53The adjacent groups in the molecule may be bonded to each other to form a saturated or unsaturated 5-membered ring 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 in the same molecule is 1 or 2. 21 ~R 53 The two or more groups represented may be the same as or different from each other.

[0030] <6> according to <1> to <5> The compound, its tautomer or a salt thereof described in any one of the above is a disazo dye.

[0031] <7> A coloring composition comprising <1> to <5> The compound described above, its tautomer or a salt thereof.

[0032] <8> according to <7> The coloring composition further contains an aqueous solvent.

[0033] <9> A dyeing method using <7> or <8> The coloring composition.

[0034] <10> A dye containing <1> to <5> The compound described above, its tautomer or a salt thereof.

[0035] <11> A sort of <1> to <6> A method for producing any one of the compounds, its tautomers or salts thereof, comprising the 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'.

[0036] [Chemical formula 5]

[0037]

[0038] 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-, R 1 , R 2a and R 2b Each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, and n represents 0, 1, 2 or 3. When n represents 2 or 3, R may be the same or different.

[0039] <12> A sort of <1> to <6> A method for producing any one of the compounds, its tautomers or salts thereof, comprising the following steps:

[0040] 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 following formula 7 with a diazonium salt represented by the following formula 8.

[0041] [Chemical formula 6]

[0042]

[0043] In Formula 5 to Formula 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-, 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 They are not aromatic hydrocarbon groups at the same time.

[0044] <13> A sort of <1> to <6> A method for producing any one of the compounds, its tautomers or salts thereof, comprising the following steps:

[0045] 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.

[0046] [Chemical formula 7]

[0047]

[0048] In Formula 5, Formula 8, and Formula 10 to Formula 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 They are not aromatic hydrocarbon groups at the same time.

[0049] <14> A sort of <1> to <6> A method for producing any one of the compounds, its tautomers or salts thereof, comprising the following steps:

[0050] 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 the formula 14 with a diazonium salt represented by the following formula 8 to obtain a compound represented by the following formula 15.

[0051] [Chemical formula 8]

[0052]

[0053] In Formula 5, Formula 8, and Formula 13 to Formula 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 Can be the same or different, R 2a With R 2b can be bonded to form a nitrogen-containing heterocyclic ring. R represents a substituent, n1 represents 0, 1, 2 or 3, and when n1 represents 2 or 3, R can be the same or different. 1 and Ar 2 They are not aromatic hydrocarbon groups at the same time.

[0054] Effects of the Invention

[0055] According to an embodiment of the present invention, a novel compound, its tautomer or a salt thereof can be provided.

[0056] According to another embodiment of the present invention, a colored composition having a hue with low chroma can be provided.

[0057] Furthermore, according to another embodiment of the present invention, there can be provided a method for producing the above-mentioned compound, its tautomer or its salt, and a dyeing method and a dyed product using the above-mentioned compound, its tautomer or its salt. DETAILED DESCRIPTION

[0058] The present invention will be described in detail below. The components described below will be described based on representative embodiments of the present invention, but the present invention is not limited to such embodiments.

[0059] In addition, in this specification, "to" which shows a numerical range is used to mean that the numerical values ​​described before and after it are included as a lower limit and an upper limit.

[0060] In the numerical ranges recorded in this specification, the upper limit or lower limit recorded in one numerical range can be replaced by the upper limit or lower limit of the numerical range recorded in other stages. In addition, in the numerical ranges recorded in this specification, the upper limit or lower limit of the numerical range can be replaced by the value shown in the embodiments.

[0061] Furthermore, in the notation of groups (atomic groups) in this specification, notation that does not describe substitution or unsubstitution includes not only groups without substitution but also groups with substitution. For example, "alkyl" includes not only alkyl groups without substitution (unsubstituted alkyl groups) but also alkyl groups with substitution (substituted alkyl groups).

[0062] Furthermore, the term "process" in this specification includes not only independent processes, but also processes that cannot be clearly distinguished from other processes as long as the desired purpose of the process can be achieved. Furthermore, in the present invention, "mass %" and "weight %" have the same meaning, and "mass parts" and "weight parts" have the same meaning.

[0063] In the present invention, a more preferred embodiment is a combination of two or more preferred embodiments.

[0064] Hereinafter, the present invention will be described in detail.

[0065] (Compound represented by Formula 1, its tautomer or its salt)

[0066] The compound, its tautomer or a salt thereof involved in the present invention is a compound represented by Formula 1, its tautomer or a salt thereof.

[0067] The compound represented by Formula 1 according to the present invention, its tautomer or a certain embodiment of a salt thereof can be preferably used as an azo dye.

[0068] Furthermore, the compound represented by Formula 1 according to the present invention, a tautomer thereof, or a certain embodiment of a salt thereof can be preferably used as a disazo dye.

[0069] The present invention includes not only the compound represented by Formula 1 but also its tautomers.

[0070] Furthermore, the compound represented by Formula 1 or its tautomer may be in the form of a salt or a mixed salt of two or more kinds.

[0071] In addition, tautomers refer to, for example, a generally known compound existing as two or more isomers that can be easily converted from one to the other, and examples thereof include isomers produced when a proton bonded to one atom in a molecule moves to another atom.

[0072] [Chemical formula 9]

[0073]

[0074] In formula 1, X- represents R 1 O-、R 2a R 2b N- or R 3 S-, R 1 , R 2a and R 2b Each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group. 2a R 2b N-, R 2a and R 2b Can be the same or different, R 2a With R 2b can be bonded to form a nitrogen-containing heterocyclic ring. R independently represents a substituent, n represents 0, 1, 2 or 3, when n represents 2 or 3, R can be the same or different. Ar represents an aromatic hydrocarbon group or a heterocyclic group, m1 represents 1, 2 or 3, when m1 represents 2 or 3, Ar can be the same or different. Wherein, at least one of Ar is a heterocyclic group.

[0075] The present inventors have conducted intensive studies and have found that by using the structure of the compound represented by the above formula 1, a novel compound, a tautomer thereof, or a salt thereof can be provided.

[0076] Furthermore, the present inventors have conducted intensive studies and found that by adopting the above-mentioned structure, a compound, a coloring composition, and a colored product having a hue with low chroma can be provided.

[0077] The mechanism of action of the excellent effect brought about by the above structure is not clear, but is presumed as follows.

[0078] The compound represented by the above formula 1, its tautomer or its salt has a phenol structure, an X-structure (i.e., R 1 O-structure, R 2a R 2b N-structure or R 3 By forming a phenol structure (S-structure), an azo group, and a heterocyclic group connected to at least one azo group, a compound with low chroma can be obtained. Furthermore, by dissociating the phenol structure (by forming a phenoxide structure), a compound with even lower chroma can be obtained.

[0079] Furthermore, it is speculated that the compound represented by the above formula 1, its tautomer or their salts can obtain a hue with low lightness and excellent hue fastness by adopting the above structure, and the absorption waveform has a wide absorption in the entire visible light region (wavelength 400nm~700nm).

[0080] Hereinafter, the compound represented by Formula 1, its tautomer or a salt thereof will be described in detail.

[0081] 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. At least one of Ar is a heterocyclic group. From the viewpoint of low chroma, low brightness and wide absorption in the visible light region, Ar is preferably a heterocyclic group independently.

[0082] The aromatic hydrocarbon group in Ar may be unsubstituted or may have a substituent. As the aromatic hydrocarbon group which may have a substituent, a phenyl group, a 1-naphthyl group or a 2-naphthyl group is preferred.

[0083] The heterocyclic group in Ar is preferably a heterocyclic group containing one or more heteroatoms selected from oxygen, sulfur and nitrogen atoms in the ring from the viewpoint of low chroma, low lightness and broad absorption in the visible light region.

[0084] From the viewpoint of low chroma, low brightness and broad absorption in the visible light region, the heterocyclic group in Ar is preferably a heterocyclic group containing a 5-membered heterocyclic ring or a 6-membered heterocyclic ring, more preferably a heterocyclic group containing a 5-membered heterocyclic ring, and particularly preferably a 5-membered heteroaromatic ring group.

[0085] Furthermore, from the viewpoint of low chroma, low brightness and broad absorption in the visible light region, the heterocyclic group in Ar is preferably a heteroaromatic ring group, more preferably a 5-membered or 6-membered heterocyclic group containing one or more heteroatoms selected from oxygen atoms, sulfur atoms and nitrogen atoms in the ring.

[0086] Furthermore, from the viewpoint of low chroma, low lightness and broad absorption in the visible light region, the heterocyclic group in 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.

[0087] The heterocyclic group in Ar may be a ring condensed with another ring. Among such condensed ring groups, a group condensed with a 5-membered ring or a 6-membered ring is preferred.

[0088] The number of carbon atoms in the heterocyclic group in Ar is preferably 2-20, more preferably 2-10.

[0089] Furthermore, 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 chroma, low lightness, and broad absorption in the visible light region.

[0090] When there are two or more Ars, the Ars may be the same group (when at least two are heterocyclic groups) or different groups, but are preferably different groups from the viewpoint of low chroma, low brightness, and broad absorption in the visible light region.

[0091] The heterocyclic group in Ar in Formula 1 is preferably a group 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 causing the compound to undergo a diazo coupling reaction with a color former (e.g., the phenol structure in Formula 1).

[0092] In other words, the heterocyclic group in Ar is a substituent which is a monovalent group obtained by removing the amino group from an amino-substituted heterocyclic compound capable of undergoing a diazotization reaction.

[0093] The aromatic hydrocarbon group and heterocyclic group in Ar in Formula 1 may have one or more substituents, and the two or more substituents may be the same or different.

[0094] Examples of the substituent include a halogen atom, a hydroxyl 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 carboxyl 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 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 imide 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 a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, an n-octyl-2-chloroethyl-2-cyanoethyl-2-ethylhexyl group, a cyclopropyl group, a cyclopentyl group), an alkenyl group (a linear, branched or cyclic alkyl group having 2 to 10 (preferably 2 to 6) carbon atoms), chain, branched or cyclic alkenyl, such as vinyl, allyl, isoprenyl, cyclopenten-1-yl), alkynyl (alkynyl having 2 to 10 (preferably 2 to 6) carbon atoms, such as ethynyl, propargyl), aryl (aryl having 6 to 12 (preferably 6 to 8) carbon atoms, such as phenyl, p-tolyl, naphthyl, 3-chlorophenyl, 2-aminophenyl), heterocyclic group (removed from a 5-membered or 6-membered aromatic or non-aromatic heterocyclic compound); a monovalent group having 1 to 12 (preferably 2 to 6) carbon atoms obtained by removing one hydrogen atom, such as 1-pyrazolyl, 1-imidazolyl, 2-furyl, 2-thienyl, 4-pyrimidinyl, 2-benzothiazolyl), cyano, hydroxyl, nitro, alkoxy (a straight-chain, branched or cyclic alkoxy group having 1 to 10 (preferably 1 to 6) carbon atoms, such as methoxy, ethoxy, isopropoxy, tert-butoxy, cyclopentyloxy, 2-butene-1-yl oxy, 2-methoxyethoxy), aryloxy (aryloxy having 6 to 12 (preferably 6 to 8) carbon atoms, such as phenoxy, 2-methylphenoxy, 4-tert-butylphenoxy, 3-nitrophenoxy), heterocyclic oxy (heterocyclic oxy having 1 to 12 (preferably 2 to 6) carbon atoms, such as 1-phenyltetrazol-5-oxy-2-tetrahydropyranyloxy), acyloxy (acyloxy having 1 to 12 (preferably 1 to 8) carbon atoms,For example, formyloxy, acetyloxy, pivaloyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy), carbamoyloxy (carbamoyloxy having 1 to 10 (preferably 1 to 6) carbon atoms, such as N,N-dimethylcarbamoyloxy, N,N-diethylcarbamoyloxy, morpholinocarbonyloxy, N,N-octylcarbamoyloxy), alkoxycarbonyloxy (alkoxycarbonyloxy having 2 to 10 (preferably 2 to 6) carbon atoms, such as methoxycarbonyloxy, ethoxycarbonyloxy, tert-butoxycarbonyloxy, n-octyloxycarbonyloxy), aryloxycarbonyloxy (aryloxycarbonyloxy having 7 to 12 (preferably 7 to 10) carbon atoms, such as phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy), amino (amino, alkylamino having 1 to 10 (preferably 1 to 6) carbon atoms, anilino having 6 to 12 (preferably 6 to 8) carbon atoms, or heterocyclic amino having 1 to 12 (preferably 2 to 6) carbon atoms, for example, including amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, imidazol-2-ylamino, pyrazol-3-ylamino), acylamino (alkylcarbonylamino having 1 to 10 (preferably 1 to 6) carbon atoms, arylcarbonylamino having 6 to 12 (preferably 6 to 8) carbon atoms, or heterocyclic carbonylamino having 2 to 12 (preferably 2 to 6) carbon atoms, for example, including

[0063] The following examples include amino, formylamino, acetylamino, pivaloylamino, benzylamino, pyridine-4-carbonylamino and thiophene-2-carbonylamino groups), aminocarbonylamino (aminocarbonylamino groups having 1 to 12 (preferably 1 to 6) carbon atoms, such as aminoformylamino, N,N-dimethylaminocarbonylamino, N,N-diethylaminocarbonylamino and morpholin-4-ylcarbonylamino), alkoxycarbonylamino (alkoxycarbonylamino groups having 2 to 10 (preferably 2 to 6) carbon atoms, such as methoxycarbonylamino, ethoxycarbonylamino and tert-butoxycarbonylamino), aryloxycarbonylamino (aryloxycarbonylamino groups having 7 to 12 (preferably 7 to 9) carbon atoms, such as phenoxycarbonylamino and p-chlorophenoxycarbonylamino groups), amino, 4-methoxyphenoxycarbonylamino), sulfamoylamino (sulfamoylamino having 0 to 10 (preferably 0 to 6) carbon atoms, for example, sulfamoylamino, N,N-dimethylaminosulfonylamino, N-(2-hydroxyethyl)sulfamoylamino), alkylsulfonylamino (alkylsulfonylamino having 1 to 10 (preferably 1 to 6) carbon atoms, for example, methylsulfonylamino, butylsulfonylamino), arylsulfonylamino (arylsulfonylamino having 6 to 12 (preferably 6 to 8) carbon atoms, for example, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino), mercapto, alkylthio (alkylthio having 1 to 10 (preferably 1 to 6) carbon atoms,For example, methylthio, ethylthio, butylthio), arylthio (arylthio having 6 to 12 (preferably 6 to 8) carbon atoms, such as phenylthio, p-chlorophenylthio, m-methoxythio), heterocyclic thio (heterocyclic thio having 2 to 10 (preferably 1 to 6) carbon atoms, such as 2-benzothiazolylthio, 1-phenyltetrazolyl-5-thio), sulfamoyl (sulfamoyl having 0 to 10 (preferably 0 to 6) carbon atoms, such as sulfamoyl, N-ethylsulfamoyl, N,N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl), alkylsulfinyl (alkylsulfinyl having 1 to 10 (preferably 1 to 6) carbon atoms, such as methylsulfinyl, ethylsulfinyl acyl), arylsulfinyl (arylsulfinyl having 6 to 12 (preferably 6 to 8) carbon atoms, such as phenylsulfinyl and p-methylphenylsulfinyl), alkylsulfonyl (alkylsulfonyl having 1 to 10 (preferably 1 to 6) carbon atoms, such as methylsulfonyl and ethylsulfonyl), arylsulfonyl (arylsulfonyl having 6 to 12 (preferably 6 to 8) carbon atoms, such as phenylsulfonyl and p-chlorophenylsulfonyl), sulfonyl, acyl (formyl, alkylcarbonyl having 2 to 10 (preferably 2 to 6) carbon atoms or arylcarbonyl having 7 to 12 (preferably 7 to 9) carbon atoms, such as acetyl, pivaloyl, 2-chloroacetyl, benzoyl, 2,4-dimethylform ... -dichlorobenzoyl), alkoxycarbonyl (alkoxycarbonyl having 2 to 10 (preferably 2 to 6) carbon atoms, for example, methoxycarbonyl, ethoxycarbonyl, tert-butoxycarbonyl, isobutoxycarbonyl), aryloxycarbonyl (aryloxycarbonyl having 7 to 12 (preferably 7 to 9) carbon atoms, for example, phenoxycarbonyl-2-chlorophenoxycarbonyl, 3-nitrophenoxycarbonyl, 4-tert-butylphenoxycarbonyl), carbamoyl (carbamoyl 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), arylazo (carbamoyl having 1 to 10 (preferably 1 to 6) carbon atoms, for example, N-methylcarbamoyl, N,N-dimethylcarbamoyl, N-(2-hydroxyethyl)carbamoyl, N-(methylsulfonyl)carbamoyl), an arylazo group having 6 to 12 (preferably 6 to 8) carbon atoms, such as phenylazo and p-chlorophenylazo), a heterocyclic azo group (a heterocyclic azo group having 1 to 10 (preferably 1 to 6) carbon atoms, such as pyrazol-3-ylazo, thiazol-2-ylazo and 5-methylthio-1,3,4-thiadiazol-2-ylazo), an imide group (an imide group having 2 to 10 (preferably 4 to 8) carbon atoms, such as succinimide and phthalimide), a phosphine group (a phosphine group having 2 to 12 (preferably 2 to 6) carbon atoms, such as dimethylphosphine, diphenylphosphine and methylphenoxyphosphine), an oxygen phosphine group (an oxygen phosphine group having 2 to 12 carbon atoms (preferably 2 to 6 carbon atoms),For example, phosphinyl, diethoxyphosphinyl), phosphinyloxy (phosphinyloxy having 2 to 12 (preferably 2 to 6) carbon atoms, such as diphenoxyphosphinyloxy, dibutoxyphosphinyloxy), phosphinylamino (phosphinylamino having 2 to 12 (preferably 2 to 6) carbon atoms, such as dimethoxyphosphinylamino, dimethylaminophosphinylamino).

[0095] When these groups are further substituted groups, these groups may further contain substituents, and as such substituents, preferably, groups having the same meanings as those described as preferred substituents for the heterocyclic group in Ar can be cited. When these groups are substituted by two or more substituents, these substituents may be the same or different.

[0096] As the substituent of the aromatic hydrocarbon group and the heterocyclic group in Ar in Formula 1, preferably a halogen atom, an alkyl group, an aryl group, a heterocyclic group, a cyano group, a hydroxyl group, a nitro group, an alkoxy group, an aryloxy group, an amino group (including an anilino group), an acylamino group, an aminocarbonylamino group, an alkoxycarbonylamino group, an alkylsulfonylamino group, an arylsulfonylamino group, an alkylthio group, an arylthio group, a heterocyclic thio group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, an alkoxycarbonyl group and a carbamoyl group, and more preferably the substituent is a halogen atom, an alkyl group, a cyano group, a hydroxyl group, a nitro group, an alkoxy group, an amino group (including an anilino group), an acylamino group, an alkylsulfonylamino group and a carbamoyl group.

[0097] From the viewpoint of low chroma, low lightness, stability of hue, and broad absorption in the visible light region, at least one of Ar is preferably a group represented by any of the following formulae (A-1) to (A-28).

[0098] Furthermore, from the viewpoint of low chroma, low lightness, fastness of hue and wide absorption in the visible light region, at least one of Ar is preferably a group represented by any of the following formulas (A-1) to (A-28), more preferably a group represented by the following formula (A-1), (A-5), (A-8), (A-9), (A-10), (A-11), (A-12), (A-13), (A-14), (A-15), (A-17), (A-19), (A-22), (A-23), (A-24) or (A-25), and particularly preferably a group represented by the following formula (A-8), (A-9), (A-10), (A-11), (A-14), (A-15), (A-22), (A-23) or (A-27).

[0099] [Chemical formula 10]

[0100]

[0101] [Chemical formula 11]

[0102]

[0103] [Chemical formula 12]

[0104]

[0105] In formulae (A-1) to (A-28), * indicates the position of bonding to the azo group in formula 1, 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 hydroxyl 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, and 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 hydroxyl 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, and R 21 ~R 53 The adjacent groups in the molecule may be bonded to each other to form a saturated or unsaturated 5-membered ring 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 in the same molecule is 1 or 2. 21 ~R 53 The two or more groups represented may be the same as or different from each other.

[0106] When R 21 ~R 53 When R is a group that can be further substituted, 21 ~R 53 It may further contain a substituent, and in this case, the substituent is the same as the substituent exemplified as the substituent of the heterocyclic group in Ar in Formula 1.

[0107] From the viewpoint of low chroma, low lightness, fastness of hue and wide absorption in the visible light region, R in Formula 1 is preferably a halogen atom, a hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group, a carboxyl 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 hydroxyl group, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an acyl group, an alkoxycarbonyl group or a carboxyl group, and particularly preferably a hydroxyl group, an alkyl group or an acyl group.

[0108] The halogen atom represented by R is preferably, for example, a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and particularly preferably a fluorine atom or a chlorine atom.

[0109] 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 tert-butyl group is preferred.

[0110] The aryl group represented by R is preferably an aryl group having 6 to 12 carbon atoms. For example, a phenyl group, a 1-naphthyl group or a 2-naphthyl group is preferred.

[0111] 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 tert-butoxy group, or a 2-methoxyethoxy group is preferred.

[0112] 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 is preferred.

[0113] 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.

[0114] 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 tert-butoxycarbonyl group or an isobutoxycarbonyl group is preferred.

[0115] 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.

[0116] As for the acylamino group represented by R, as an alkylcarbonylamino group, an alkylcarbonylamino group having 1 to 10 carbon atoms is preferred, and an alkylcarbonylamino group having 1 to 6 carbon atoms is particularly preferred. Furthermore, as an arylcarbonylamino group, an arylcarbonylamino group having 6 to 12 carbon atoms is preferred, and an arylcarbonylamino group having 6 to 8 carbon atoms is particularly preferred. Alternatively, as a heterocyclic carbonylamino group, a heterocyclic carbonylamino group having 2 to 12 carbon atoms is preferred, and a heterocyclic carbonylamino group having 2 to 6 carbon atoms is particularly preferred. For example, formylamino, acetylamino, pivaloylamino, benzylamino, pyridine-4-carbonylamino, thiophene-2-carbonylamino, and the like are preferred.

[0117] As for the sulfonylamino group represented by R, as an alkylsulfonylamino group, an alkylsulfonylamino group having 1 to 10 carbon atoms is preferred, and an alkylsulfonylamino group having 1 to 6 carbon atoms is particularly preferred. Furthermore, as an arylsulfonylamino group, an arylsulfonylamino group having 6 to 12 carbon atoms is preferred, and an arylsulfonylamino group having 6 to 8 carbon atoms is particularly preferred. For example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, or p-methylphenylsulfonylamino is preferred.

[0118] 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, N-ethylsulfamoyl group, N,N-dimethylsulfamoyl group, N-acetylsulfamoyl group or N-benzoylsulfamoyl group is preferred.

[0119] 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.

[0120] 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 a m-methoxyphenylthio group is preferred.

[0121] 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.

[0122] 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.

[0123] When n is 2, two Rs may be bonded to form a ring. The formed ring is preferably a 5-membered or 6-membered ring. The formed ring may be any of saturated and unsaturated, but is preferably unsaturated. The formed ring may be any of a hydrocarbon ring and a heterocyclic ring, but is preferably an aromatic hydrocarbon ring or a heteroaromatic ring. Examples of the formed ring are preferably a cyclohexene ring, a benzene ring, a naphthalene ring, a pyrrole ring or a pyrazole ring. A benzene ring or a pyrrole ring is particularly preferred.

[0124] In formula 1, X- represents R 1 O-、R 2a R 2b N- or R 3 S-, R 1 , R 2a and R 2b Each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group. 2a R 2b N-, R 2a and R 2b Can be the same or different, R 2a With R 2b From the viewpoint of low chroma and low brightness, X- is more preferably R 1 O- and R 2a R 2b N-.

[0125] In formula 1, R 1 , R 2a , R 2b or R 3 The alkyl group represented 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 tert-butyl group is preferred.

[0126] From the perspective of low chroma, low brightness, water solubility, and wide absorption in the visible light region, R in Formula 1 1 , R 2a and R 2b Preferred is a hydrogen atom or a methyl group.

[0127] When X- represents R 2a R 2b N-, R 2a R 2b N- may be any of an amino group (H2N-), a monoalkyl-substituted amino group and a dialkyl-substituted amino group.

[0128] As X-represents R 2a R 2b N-, R 2a With R 2bWhen the nitrogen-containing heterocyclic ring is bonded to form a nitrogen-containing heterocyclic ring, the nitrogen-containing heterocyclic ring is preferably a 5-membered or 6-membered nitrogen-containing heterocyclic ring. Examples of the nitrogen-containing heterocyclic ring include a pyrrolidine ring, a piperidine ring, a morpholine ring, and a piperazine ring.

[0129] X-(i.e. R 1 O-、R 2a R 2b N- or R 3 The bonding position of S-) is not particularly limited, but is preferably the meta position relative to the hydroxyl group from the viewpoints of low chroma, low lightness, stability of hue, and broad absorption in the visible light region.

[0130] From the viewpoint of low chroma, low lightness, stability of hue, and broad absorption in the visible light region, m1 in Formula 1 is preferably 2 or 3, and more preferably 2.

[0131] From the viewpoint of low chroma, low lightness, fastness of hue, and broad absorption in the visible light region, n in Formula 1 is preferably 0, 1, or 2, and more preferably 0 or 1.

[0132] When the compound represented by Formula 1 forms a salt, it is preferably formed with a monovalent or divalent cation. As the monovalent cation, an alkali metal cation (e.g., lithium cation, sodium cation, potassium cation), an ammonium cation (e.g., ammonium cation, trimethylammonium cation, triethylammonium cation, tetramethylammonium cation) is preferred. As the divalent cation, an alkaline earth metal cation (e.g., calcium cation) is preferred.

[0133] The compound represented by Formula 1 includes a compound represented by any of the following Formulas A1 to A3.

[0134] [Chemical formula 13]

[0135]

[0136] In formula A1, X- represents R 1 O-、R 2a R 2b N- or R 3 S-, R 1 , R 2a and R 2b Each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, when X- is R 2a R 2b N-, R 2a and R 2b Can be the same or different, R 2a With R 2b They can be bonded to form a nitrogen-containing heterocyclic ring. 1 and Ar 2Each independently represents an aromatic hydrocarbon group or a heterocyclic group, and R each independently represents a substituent. n1 represents 0, 1 or 2. When n1 represents 2, R may be the same or different. 1 and Ar 2 They are not aromatic hydrocarbon groups at the same time.

[0137] In formula A2, X- represents R 1 O-、R 2a R 2b N- or R 3 S-, R 1 , R 2a and R 2b Each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, when X- is R 2a R 2b N-, R 2a and R 2b N- can be the same or different, R 2a With R 2b They may be bonded to form a nitrogen-containing heterocyclic ring. n2 represents 0 or 1. Ar 1 ,Ar 2 and Ar 3 Each independently represents an aromatic hydrocarbon group or a heterocyclic group. 1 and Ar 2 They are not aromatic hydrocarbon groups at the same time.

[0138] In formula A3, X- represents R 1 O-、R 2a R 2b N- or R 3 S-, R 1 , R 2a and R 2b Each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, when X- is R 2a R 2b N-, R 2a and R 2b N- can be the same or different, R 2a With R 2b They may be bonded to form a nitrogen-containing heterocyclic ring. n3 represents 0, 1, 2 or 3. When n3 represents 2 or 3, R may be the same or different. 11 It represents a heterocyclic group.

[0139] Ar in Formula A1 to Formula A3 1 ,Ar 2 ,Ar 3 and Ar 11 Each independently has the same meaning as Ar in Formula 1, and the preferred embodiments are also the same.

[0140] R and R in Formulas A1 to A3 2a and R 2b Respectively with R and R in formula 1 2a and R 2b The meanings are the same and the preferred aspects are also the same.

[0141] From the viewpoint of low chroma, low lightness, stability of hue, and broad absorption in the visible light region, n1 in formula A1 is preferably independently 0 or 1.

[0142] From the viewpoint of low chroma, low lightness, stability of hue, and broad absorption in the visible light region, n2 in formula A2 is preferably 0, respectively, independently.

[0143] From the viewpoint of low chroma, low lightness, fastness of hue and broad absorption in the visible light region, n3 in formula A3 is preferably 0, 1 or 2, more preferably 0 or 1, and further preferably 0.

[0144] From the viewpoint of low chroma, low brightness, hue fastness and wide absorption in the visible light region, the compound represented by Formula 1 is preferably a compound represented by any of the following formulas A1-1 to A1-3, A2-1 to A2-3 and A3-1 to A3-3, more preferably a compound represented by any of the following formulas A1-1 to A1-3 and A2-1 to A2-3, and further preferably a compound represented by any of the following formulas A1-1, A1-2 and A1-3.

[0145] [Chemical formula 14]

[0146]

[0147] In formula A1-1 to formula A1-3, X- represents R 1 O-、R 2a R 2b N- or R 3 S-, R 1 , R 2a and R 2b Each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, when X- is R 2a R 2b N-, R 2a and R 2b N- can be the same or different, R 2a With R 2b They can be bonded to form a nitrogen-containing heterocyclic ring. 1 and Ar 2Each independently represents an aromatic hydrocarbon group or a heterocyclic group, and R each independently represents a substituent. n1 represents 0, 1 or 2. When n1 represents 2, R may be the same or different. 1 and Ar 2 They are not aromatic hydrocarbon groups at the same time.

[0148] In formula A2-1 to formula A2-3, X- represents R 1 O-、R 2a R 2b N- or R 3 S-, R 1 , R 2a and R 2b Each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, when X- is R 2a R 2b N-, R 2a and R 2b N- can be the same or different, R 2a With R 2b They may be bonded to form a nitrogen-containing heterocyclic ring. n1 represents 0 or 1. Ar 1 ,Ar 2 and Ar 3 Each independently represents an aromatic hydrocarbon group or a heterocyclic group. 1 and Ar 2 They are not aromatic hydrocarbon groups at the same time.

[0149] In formula A3-1 to formula A3-3, X- represents R 1 O-、R 2a R 2b N- or R 3 S-, R 1 , R 2a and R 2b Each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, when X- is R 2a R 2b N-, R 2a and R 2b N- can be the same or different, R 2a With R 2b They may be bonded to form a nitrogen-containing heterocyclic ring. n3 represents 0, 1, 2 or 3. When n3 represents 2 or 3, R may be the same or different. 11 It represents a heterocyclic group.

[0150] Ar in Formula A1-1 to Formula A1-3 1 ,Ar 2 , R, R 1 , R 2a , R 2b , R3 and n1 are respectively the same as Ar in formula A1 1 ,Ar 2 , R, R 1 , R 2a , R 2b , R 3 and n1 have the same meanings and the preferred aspects are also the same.

[0151] 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 respectively the same as Ar in formula A2 1 ,Ar 2 ,Ar 3 , R 1 , R 2a , R 2b and R 3 The meanings are the same and the preferred aspects are also the same.

[0152] Ar in Formula A3-1 to Formula A3-3 11 , R 1 , R 2a , R 2b , R 3 and n3 are respectively the same as Ar in formula A3 11 , R 1 , R 2a , R 2b and R 3 The meanings are the same and the preferred aspects are also the same.

[0153] When X- in formula A1 represents R 1 O-, from the viewpoint of low chroma, low lightness, fastness of hue and wide absorption in the visible light region, among the compounds represented by formula A1, Ar 1 and Ar 2 are independently a heterocyclic group, R 1 is a hydrogen atom, R is a hydroxyl group, an alkyl group or an acyl group, and n1 is 0 or 1, more preferably Ar 1 is a heterocyclic group having a sulfur atom, Ar 2 For Ar 1 Different heterocyclic groups, R 1 is a hydrogen atom, R is a hydroxyl group, an alkyl group or an acyl group, and n1 is 0 or 1, and Ar is particularly preferred 1 is a heterocyclic group having a sulfur atom and a nitrogen atom, Ar 2 For Ar 1 Different heterocyclic groups, R 1is a hydrogen atom, R is a hydroxyl group, an alkyl group or an acyl group, and n1 is 0 or 1.

[0154] When X- in formula A1 represents R 2a R 2b When N-, from the viewpoint of low chroma, low lightness, fastness of hue and wide absorption in the visible light region, among the compounds represented by formula A1, Ar 1 and Ar 2 are independently a heterocyclic group, R 2a and R 2 b are each independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R 2a and R 2b When the nitrogen-containing heterocyclic ring is formed by bonding, it is pyrrolidinyl, piperidinyl or morpholinyl, R is a halogen atom (such as a chlorine atom) or a methyl group, and n1 is 0 or 1, and Ar is more preferred. 1 is a 5-membered heterocyclic group or a 5- to 6-membered fused heterocyclic group, Ar 2 is a 5-membered heterocyclic group, a 5-membered to 6-membered fused heterocyclic group or an aromatic hydrocarbon group, R 2a is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-butyl or tert-butyl), R 2b is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-butyl or tert-butyl), R is a hydrogen atom or a methyl group, and n1 is 0 or 1, and Ar is particularly preferred. 1 is a 5-membered heterocyclic group or a 5- to 6-membered fused heterocyclic group, Ar 2 is a 5-membered heterocyclic group or a 5- to 6-membered fused-ring heterocyclic group, R 2a is a hydrogen atom or a methyl group, R 2b is a hydrogen atom or a methyl group, R is a chlorine atom or a methyl group, and n1 is 0 or 1.

[0155] When X- in formula A1 represents R 3 In the case of S-, from the viewpoint of low chroma, low lightness, fastness of hue and wide absorption in the visible light region, among the compounds represented by formula A1, Ar 1 and Ar 2 are independently a heterocyclic group, R 3 is an alkyl group having 1 to 4 carbon atoms, R is a halogen atom (such as a chlorine atom) or a methyl group, and n1 is 0 or 1, and Ar is more preferably 1 is a 5-membered heterocyclic ring or a 5- to 6-membered condensed heterocyclic ring, Ar 2 is a 5-membered heterocyclic group, a 5-membered to 6-membered fused heterocyclic group or an aromatic hydrocarbon group, 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, and Ar is particularly preferred 1 is a 5-membered heterocyclic ring or a 5- to 6-membered condensed heterocyclic ring, Ar 2is a 5-membered heterocyclic ring or a 5- to 6-membered fused heterocyclic ring, R 3 is a methyl group, R is a chlorine atom or a methyl group, and n1 is 0 or 1.

[0156] When X- in formula A2 represents R 1 O-, from the viewpoint of low chroma, low lightness, fastness of hue and wide absorption in the visible light region, among the compounds represented by formula A2, Ar 1 ,Ar 2 ,Ar 3 are independently a heterocyclic group, R 1 is a hydrogen atom or a methyl group, an ethyl group, or a hydroxyethyl group, R is a halogen atom (such as a chlorine atom) or a methyl group, and n2 is 0 or 1, preferably Ar 1 is a 5-membered heterocyclic ring or a 5- to 6-membered condensed heterocyclic ring, Ar 2 is a 5-membered heterocyclic ring or a 5- to 6-membered condensed heterocyclic ring, Ar 3 is a 5-membered heterocyclic group, a 5-membered to 6-membered fused heterocyclic group or an aromatic hydrocarbon group, R 1 is a hydrogen atom or a methyl group, R is a chlorine atom or a methyl group, and n2 is 0 or 1, preferably Ar 1 is a 5-membered heterocyclic ring, Ar 2 is a 5-membered heterocyclic ring or a 5- to 6-membered condensed heterocyclic ring, Ar 3 is a 5-membered heterocyclic ring or a 5- to 6-membered fused heterocyclic ring, R 1 is a hydrogen atom or a methyl group, and n2 is 0.

[0157] When X- in formula A2 represents R 2a R 2b When N-, from the viewpoint of low chroma, low lightness, fastness of hue and wide absorption in the visible light region, among the compounds represented by formula A2, Ar 1 ,Ar 2 ,Ar 3 are independently a heterocyclic group, R 2a and R 2b are independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R 2a and R 2b When the nitrogen-containing heterocyclic ring is formed by bonding, it is pyrrolidinyl, piperidinyl, morpholinyl, R is a halogen atom (such as a chlorine atom) or a methyl group, and n2 is 0 or 1, and Ar is more preferred. 1 is a 5-membered heterocyclic ring or a 5- to 6-membered condensed heterocyclic ring, Ar 2 is a 5-membered heterocyclic ring or a 5- to 6-membered condensed heterocyclic ring, Ar 3 is a 5-membered heterocyclic group, a 5-membered to 6-membered fused heterocyclic group or an aromatic hydrocarbon group, R 2a is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-butyl or tert-butyl), R 2bis a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-butyl or tert-butyl), R is a chlorine atom or a methyl group, and n2 is 0 or 1, and Ar is particularly preferred. 1 is a 5-membered heterocyclic group, Ar 2 is a 5-membered heterocyclic group or a 5- to 6-membered fused heterocyclic group, Ar 3 is a 5-membered heterocyclic group or a 5- to 6-membered fused-ring heterocyclic group, R 2a is a hydrogen atom or a methyl group, R 2b is a hydrogen atom or a methyl group, and n2 is 0.

[0158] When X- in formula A2 represents R 3 When S-, from the viewpoint of low chroma, low lightness, fastness of hue and wide absorption in the visible light region, among the compounds represented by formula A2, Ar 1 and Ar 2 ,Ar 3 are independently a heterocyclic group, 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, and Ar is more preferred 1 is a 5-membered heterocyclic group or a 5- to 6-membered fused heterocyclic group, Ar 2 is a 5-membered heterocyclic group or a 5- to 6-membered fused heterocyclic group, Ar 3 is a 5-membered heterocyclic group, a 5-membered to 6-membered fused heterocyclic group or an aromatic hydrocarbon group, 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, and Ar is particularly preferred 1 is a 5-membered heterocyclic group, Ar 2 is a 5-membered heterocyclic group or a 5- to 6-membered fused heterocyclic group, Ar 3 is a 5-membered heterocyclic group or a 5- to 6-membered fused-ring heterocyclic group, R 3 is methyl, and n2 is 0.

[0159] When X- in formula A3 represents R 1 O-, from the viewpoint of low chroma, low lightness, fastness of hue and wide absorption in the visible light region, among the compounds represented by formula A3, Ar 11 is a heterocyclic group, R 1 is a hydrogen atom or a methyl group, an ethyl group, or a hydroxyethyl group, R is a halogen atom (such as a chlorine atom) or a methyl group, and n3 is 0 or 1, and more preferably Ar 11 is a 5-membered heterocyclic group or a 5- to 6-membered fused-ring heterocyclic group, 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, and Ar is particularly preferred 11 is a 5-membered heterocyclic group or a 5- to 6-membered fused-ring heterocyclic group, R 1 is a hydrogen atom or a methyl group, and n3 is 0.

[0160] When X- in formula A3 represents R 2a R 2b When N-, from the viewpoint of low chroma, low lightness, fastness of hue and wide absorption in the visible light region, among the compounds represented by formula A3, Ar 11 is a heterocyclic group, R 2a and R 2b are independently a hydrogen atom or an alkyl group having 1 to 12 carbon atoms, R 2a and R 2b When the nitrogen-containing heterocyclic ring is formed by bonding, it is pyrrolidinyl, piperidinyl, morpholinyl, R is a chlorine atom or a methyl group, and n3 is 0 or 1, and Ar is more preferred. 11 is a 5-membered heterocyclic group or a 5- to 6-membered fused-ring heterocyclic group, R 2a is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-butyl or tert-butyl), R 2b is a hydrogen atom or an alkyl group having 1 to 4 carbon atoms (e.g., methyl, ethyl, n-butyl or tert-butyl), R is a chlorine atom or a methyl group, and n3 is 0 or 1, and Ar is particularly preferred. 11 is a 5-membered heterocyclic group or a 5- to 6-membered fused-ring heterocyclic group, R 2a is a hydrogen atom or a methyl group, R 2b is a hydrogen atom or a methyl group, R is a chlorine atom or a methyl group, and n3 is 0 or 1.

[0161] When X- in formula A3 represents R 3 When S-, from the viewpoint of low chroma, low lightness, fastness of hue and wide absorption in the visible light region, among the compounds represented by formula A3, Ar 11 is a heterocyclic group, R 3 is an alkyl group having 1 to 4 carbon atoms, R is a chlorine atom or a methyl group, and n3 is 0 or 1, preferably Ar 11 is a 5-membered heterocyclic group or a 5- to 6-membered fused-ring heterocyclic group, R 3 is an alkyl group having 1 to 4 carbon atoms, R is a chlorine atom or a methyl group, and n3 is 0 or 1, and Ar is particularly preferred 11 is a 5-membered heterocyclic group or a 5- to 6-membered fused-ring heterocyclic group, R 3 is methyl, and n3 is 0.

[0162] Specific examples of the compound represented by Formula 1 are described below, but the present invention is not limited to these examples. In addition, Me represents a methyl group, and Et represents an ethyl group (the same below).

[0163] [Chemical formula 15]

[0164]

[0165] [Chemical formula 16]

[0166]

[0167] [Chemical formula 17]

[0168]

[0169] [Chemical formula 18]

[0170]

[0171] [Chemical formula 19]

[0172]

[0173] [Chemical formula 20]

[0174]

[0175] [Chemical formula 21]

[0176]

[0177] [Chemical formula 22]

[0178]

[0179] [Chemical formula 23]

[0180]

[0181] [Chemical formula 24]

[0182]

[0183] [Chemical formula 25]

[0184]

[0185] [Chemical formula 26]

[0186]

[0187] [Chemical formula 27]

[0188]

[0189] [Chemical formula 28]

[0190]

[0191] [Chemical formula 29]

[0192]

[0193] [Chemical formula 30]

[0194]

[0195] The method for producing the compound represented by Formula 1, its tautomer and a salt thereof is not particularly limited, and for example, they can be synthesized by the method described in JP-A-2017-515930.

[0196] In one embodiment of the method for producing the compound represented by Formula 1, its tautomers and salts thereof, it preferably includes a step of reacting a diazonium salt represented by Formula 5' with a compound represented by Formula 6 to obtain a compound represented by Formula 7' (also referred to as "diazotization step 1').

[0197] [Chemical formula 31]

[0198]

[0199] 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-, R 1 , R 2a and R 2b Each independently represents a hydrogen atom or an alkyl group, R 3 represents an alkyl group, and n represents 0, 1, 2 or 3. When n represents 2 or 3, R may be the same or different.

[0200] Furthermore, in a certain mode of the method for producing the compound represented by Formula 1, its tautomer and its salt, it is preferred to include a step (diazotization step 1) of reacting a diazonium salt represented by Formula 5 with a compound represented by Formula 6 to obtain a compound represented by Formula 7; 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. That is, the method for producing the compound represented by Formula 1, its tautomer and its salt may also include the following mode: using a compound represented by Formula 7, i.e., a diazonium salt, as an intermediate and reacting it with a diazonium salt represented by Formula 8.

[0201] [Chemical formula 32]

[0202]

[0203] In Formula 5 to Formula 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-、R1 S- or R 1 R 2 N-, R 1 and R 2 Each independently represents a hydrogen atom or an alkyl group, and n represents 0, 1, 2 or 3. When n represents 2 or 3, R may be the same or different. 1 and Ar 2 They are not aromatic hydrocarbon groups at the same time.

[0204] In a certain embodiment of the method for producing the compound represented by Formula 1, its tautomers and their salts, it is more preferable to include 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 (also referred to as "diazotization step 3") and a step of reacting the obtained compound represented by the following Formula 11 with a diazonium salt represented by the following Formula 8 to obtain a compound represented by the following Formula 12 (also referred to as "diazotization step 4").

[0205] [Chemical formula 33]

[0206]

[0207] In Formula 5, Formula 8, and Formula 10 to Formula 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 They are not aromatic hydrocarbon groups at the same time.

[0208] Furthermore, in a certain embodiment of the method for producing the compound represented by Formula 1, its tautomers and their salts, it is preferably included 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 (also referred to as "diazotization step 5") and a step of reacting the obtained compound represented by the following Formula 14 with a diazonium salt represented by the following Formula 8 to obtain a compound represented by the following Formula 15 (also referred to as "diazotization step 6").

[0209] [Chemical formula 34]

[0210]

[0211] In Formula 5, Formula 8, and Formula 13 to Formula 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 R2 Can be the same or different, R 1 and R 2 can be bonded to form a nitrogen-containing heterocyclic ring. R represents a substituent, n1 represents 0, 1 or 2, when n1 represents 2, R can be the same or different, wherein Ar 1 and Ar 2 They are not aromatic hydrocarbon groups at the same time.

[0212] Ar in Formula 5' and Formula 7' 11 It has the same meaning as Ar in Formula 1, and the preferred aspects are also the same.

[0213] Ar in Formula 5 and Formula 7 to Formula 8 1 and Ar 2 They have the same meanings as Ar in Formula 1, and their preferred embodiments are also the same.

[0214] 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 preferred aspects are also the same.

[0215] Ar in Formula 10 to Formula 12 1 ,Ar 2 , R, R 1 and n1 are respectively the same as Ar in formula A1 1 ,Ar 2 , R, R 1 and n1 have the same meanings and the preferred aspects are also the same.

[0216] Ar in Formula 13 to Formula 15 1 ,Ar 2 , R, R 2a , R 2b and n1 are respectively the same as Ar in formula A1 1 ,Ar 2 , R, R 2a , R 2b and n1 have the same meanings and the preferred aspects are also the same.

[0217] There are no particular limitations on the method for preparing the diazonium salt represented by Formula 5', Formula 5 or Formula 8, and the diazonium salt may be prepared by a known method or with reference to a known method. Specifically, for example, a method of preparing the diazonium salt by reacting sodium nitrite or nitrosylsulfuric acid with an amino group of an amine compound is preferred.

[0218] Furthermore, the counter anion of the diazonium salt represented by Formula 5 or Formula 8 is not particularly limited, and a known anion can be used.

[0219] In addition, in the above-mentioned diazotization step 1' and diazotization steps 1 to 6, known diazo coupling reaction conditions (eg, reaction temperature, reaction time, reaction solvent, etc.) can be used.

[0220] 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 according to the rarity and reactivity of each reaction substrate.

[0221] <Purpose>

[0222] 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.

[0223] Furthermore, the compound represented by Formula 1, its tautomer and salts thereof, or the coloring composition has a special hue with low chroma and can therefore be preferably used as a pigment, more preferably as a coloring agent.

[0224] In addition, the use of the compound represented by Formula 1, its tautomer and its salts include black matrices used in displays such as liquid crystal displays (LCDs) and plasma display panels (PDPs), curable compositions for preparing these black matrices, color image recording materials for forming color images, etc. Specifically, it can be used for inkjet recording materials (such as inkjet recording inks), sublimation-type thermosensitive recording materials, recording materials using electronic photography (such as color toners), transfer-type silver halide photosensitive materials, printing inks, recording pens, fiber dyeing, etc., preferably for inkjet recording materials, transfer-type silver halide photosensitive materials, printing inks, fiber dyeing, etc.

[0225] The compound represented by Formula 1, its tautomer or its salt can be optimized and used by adjusting the substituents to optimize the solubility, dispersibility and other physical properties suitable for its use. In addition, the compound represented by Formula 1, its tautomer or its salt can also be used in a dissolved state, an emulsified dispersion state, or a solid dispersion state according to the system used.

[0226] (Coloring composition)

[0227] The coloring composition according to the present invention contains the compound represented by Formula 1, its tautomer, or a salt thereof, and preferably further contains an aqueous solvent from the viewpoint of dyeing properties.

[0228] The coloring composition according to the present invention may contain one kind of the compound represented by Formula 1, its tautomer, or a salt thereof, or may contain two or more kinds thereof, and may also be combined with other direct dyes or disperse dyes.

[0229] The coloring composition according to the present invention may contain a medium.

[0230] The coloring composition involved in the present invention can be prepared by using a lipophilic medium and / or an aqueous medium as a medium, and dissolving and / or dispersing therein at least one selected from the compound represented by Formula 1, its tautomers, and salts thereof. The case of using an aqueous medium is preferred, and the case of using an aqueous solvent is more preferred.

[0231] The content of the compound represented by Formula 1, its tautomer, and its salt contained in the coloring composition of the present invention is determined by the type of substituents in the compound represented by Formula 1, its tautomer, and its salt used, and the type of solvent component used to produce the coloring composition. The content of the compound represented by Formula 1, its tautomer, and its salt in the coloring composition is preferably 0.001% by mass to 30% by mass, more preferably 0.001% by mass to 20% by mass, further preferably 0.1% by mass to 10% by mass, and particularly preferably 0.5% by mass to 10% by mass.

[0232] By making the content of the compound represented by Formula 1, its tautomer and its salt 0.001% by mass or more, the coloring concentration of the pigment on the colored medium can be ensured. In addition, by making the content of the compound represented by Formula 1, its tautomer and its salt 30% by mass or less, a low-viscosity coloring composition can be prepared, and the handling becomes easy.

[0233] When the coloring composition involved in the present invention contains an aqueous solvent (preferably water), it can be used at any pH, but from the viewpoint of the stability and dyeing properties of the compound, the pH range is preferably 5 to 11, more preferably 6 to 11, and from the viewpoint of the stability and dyeing properties of the compound represented by Formula 1, its tautomers, and their salts, the pH range is particularly preferably 7 to 11.

[0234] In addition, the pH value in the present invention is a value at 25°C.

[0235] The coloring composition according to the present invention may contain a pH adjuster.

[0236] Examples of the pH adjuster used in the coloring composition of the present invention include sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, potassium hydrogen carbonate, ammonia, monoethanolamine, diethanolamine, and guanidine.

[0237] The coloring composition of the present invention may contain a surfactant. Examples of surfactants that can be used include anionic surfactants, nonionic surfactants, cationic surfactants, and amphoteric or diionic surfactants. Furthermore, the above surfactants may be used alone or in combination of two or more.

[0238] Examples of anionic surfactants that can be used in the coloring composition of the present invention include monoalkyl sulfuric acid or its salt, alkylbenzenesulfonic acid or its salt, α-olefin sulfonate or its salt, and in particular sodium dodecylbenzenesulfonate, sodium dodecyl sulfate, alkali salts of sulfosuccinic acid half esters such as monooctylsulfosuccinic acid disodium salt, and chain monoalkylethoxysulfosuccinic acid alkali salts.

[0239] Examples of the nonionic surfactant that can be used in the coloring composition of the present invention include alkyl polyglycosides, sorbitan esters, and acetylene glycols.

[0240] As the cationic surfactant that can be used in the coloring composition involved in the present invention, quaternary ammonium compounds can be preferably mentioned, and 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) can be more preferably mentioned. As examples, hexadecyltrimethylammonium chloride, dimethylstearylammonium chloride, trimethylacetylammonium bromide, stearyltrimethylammonium chloride, dimethylstearylbenzylammonium chloride, benzyltetradecyldimethylammonium chloride, dimethyldihydrogenated tallow ammonium chloride, lauryldimethylbenzylammonium chloride, behenyltrimethylammonium chloride, lauryltrimethylammonium chloride, tri(oligooxy-ethyl)alkylammonium phosphate, cetylpyridinium chloride, etc. can be mentioned.

[0241] Examples of the amphoteric or diionic surfactant that can be used in the coloring composition of the present invention include betaines such as fatty acid-amidoalkyl betaine or sulfobetaine (for example, lauryl hydroxysulfobetaine).

[0242] When the coloring composition according to the present invention is used as an aqueous coloring composition, the coloring composition according to the present invention preferably contains an aqueous solvent.

[0243] Examples of the aqueous solvent include water, organic solvents soluble in water (preferably soluble at 25° C.), and mixed solvents thereof.

[0244] As the aqueous solvent that can be used, there can be mentioned 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, etc. Among them, 1,2- or 1,3-propylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, 1,3- or 1,4-butanediol, diethylene glycol, monomethyl or monoethyl ether of diethylene glycol, dipropylene glycol or monomethyl or monoethyl ether of dipropylene glycol are preferred.

[0245] When the coloring composition involved in the present invention is used as an aqueous coloring composition, the content of the compound represented by Formula 1, its tautomer and its salt is preferably 0.001% by mass to 30% by mass, more preferably 0.001% by mass to 20% by mass, further 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.

[0246] Furthermore, as the aqueous solvent, monohydric alcohols such as methanol, ethanol, isopropanol, and n-propanol; polyhydric alcohols such as glycerol and hexanetriol; ethyl carbitol; benzyl alcohol; benzyloxyethanol; propylene carbonate (4-methyl-1,3-dioxane-2-one); n-alkyl pyrrolidone; and urea can be used in combination.

[0247] The coloring composition according to the present invention may contain a thickener.

[0248] Examples of the thickener include oleic acid, cetyl alcohol, oleyl alcohol, sodium chloride, cetearyl alcohol, and stearyl alcohol.

[0249] 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.

[0250] The coloring composition according to the present invention may contain other coloring compounds (pigments, dyes, etc.) in addition to the compound represented by Formula 1, its tautomers, and salts thereof.

[0251] As the yellow dye that can be used, any yellow dye can be used, for example, there are aromatic or heterocyclic azo dyes, azomethine dyes, methine dyes, quinone dyes, etc., and as dye types other than these, quinophthalone dyes, nitro and nitroso dyes, acridine dyes, acridone dyes, etc. can be cited.

[0252] As the usable magenta dye, any magenta dye can be used, and examples thereof include aromatic or heterocyclic 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.

[0253] As the cyan dye that can be used, any cyan dye can be used, for example, aromatic or heterocyclic azo dyes, azomethine dyes, polymethine dyes such as cyanine dyes, oxonol dyes, and merocyanine dyes, diphenylmethane dyes, triphenylmethane dyes, carbonium dyes such as xanthene dyes, phthalocyanine dyes, anthraquinone dyes, indigo / thioindigo dyes, etc. can be mentioned.

[0254] Furthermore, a black dye may be contained. Usable black dyes include disazo, trisazo, and tetrakisazo dyes, and dispersions of carbon black.

[0255] Furthermore, the coloring composition according to the present invention 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.

[0256] Examples of other additives that can be used in the coloring composition according to the present invention include silicone oil, hydrocarbon oil, polyolefin, and fatty acid ester.

[0257] The coloring composition of the present invention may further contain other additives as needed within a range that does not impair the effects of the present invention. Examples of additives for each application will be described later.

[0258] <Color toner>

[0259] When the coloring composition involved in the present invention is used as a color toner, the content of the compound represented by Formula 1, its tautomer and its salt in the coloring composition for color toner is preferably 0.1 parts by mass or more, more preferably 1 part by mass to 20 parts by mass, and particularly preferably 2 parts by mass to 10 parts by mass, when the coloring composition for color toner is 100 parts by mass.

[0260] When the coloring composition according to the present invention is used for color toners, the coloring composition for color toners preferably contains a binder resin.

[0261] As the binder resin, any generally used binder can be used, for example, styrene resins, acrylic resins, styrene / acrylic resins, polyester resins, etc. can be mentioned.

[0262] When the coloring composition of the present invention is used as a color toner, inorganic particles and / or organic particles may be added externally for the purpose of fluidity, charge control, etc. of the coloring composition for color toner. For example, preferably, silica particles or titanium dioxide particles whose surfaces are treated with an alkyl-containing coupling agent or the like. In addition, their number average primary particle diameter is preferably 10 nm to 500 nm, and preferably 0.1 mass % to 20 mass % are added to the toner.

[0263] When the coloring composition according to the present invention is used for color toners, the coloring composition for color toners preferably contains a release agent.

[0264] As the release agent, any conventionally used release agent can be used, and specific examples thereof include polyolefins such as low molecular weight polypropylene, low molecular weight polyethylene, and ethylene-propylene copolymers, microcrystalline wax, carnauba wax, Sasol wax, and paraffin wax.

[0265] The content of the releasing agent is preferably 1% by mass to 5% by mass based on the total mass of the color toner composition.

[0266] When the coloring composition according to the present invention is used for color toners, the coloring composition for color toners preferably contains a charge control agent.

[0267] Examples of the charge control agent include quaternary ammonium salt compounds and calixarene compounds.

[0268] When the coloring composition according to the present invention is used as a color toner, the coloring composition for a color toner may contain a carrier.

[0269] As the carrier, either an uncoated carrier consisting only of magnetic material particles such as iron and ferrite or a resin-coated carrier in which the surface of magnetic material particles is coated with a resin or the like can be used.

[0270] The average particle size of the carrier is preferably 30 μm to 150 μm in terms of volume average particle size.

[0271] <Ink for inkjet recording>

[0272] When the coloring composition of the present invention is used as an inkjet recording ink, the inkjet recording ink is preferably an ink obtained by dissolving and / or dispersing the coloring composition in a lipophilic medium or an aqueous medium, and more preferably an ink using an aqueous medium (preferably an aqueous solvent).

[0273] When the coloring composition involved in the present invention is used as an ink for inkjet recording, the inkjet recording ink may contain known additives such as an anti-drying agent (wetting agent), an anti-fading agent, an emulsion stabilizer, a penetration promoter, an ultraviolet absorber, a preservative, an antifungal agent, a pH adjuster, a surface tension adjuster, a defoaming agent, a viscosity adjuster, a dispersant, a dispersion stabilizer, a rust inhibitor, and a chelating agent as needed.

[0274] In the case of water-soluble inks, these various additives are directly added to the ink liquid. When an oil-soluble dye is used in the form of a dispersion, it is generally added to the dispersion after the dye dispersion is prepared, but it can also be added to the oil phase or the water phase during preparation.

[0275] The anti-drying agent is preferably used for the purpose of preventing clogging of the ink ejection openings of the nozzles used in the ink jet recording method due to drying of the ink for ink jet recording.

[0276] As an anti-desiccant, a water-soluble organic solvent having a vapor pressure lower than that of water is preferred. As specific examples, polyols represented by ethylene glycol, propylene glycol, diethylene glycol, polyethylene glycol, thiodiglycol, dithiodiglycol, 2-methyl-1,3-propanediol, 1,2,6-hexanetriol, acetylene glycol derivatives, glycerol, trimethylolpropane, etc., lower alkyl ethers of polyols such as ethylene glycol monomethyl (or ethyl) ether, diethylene glycol monomethyl (or ethyl) ether, triethylene glycol monoethyl (or butyl) ether, 2-pyrrolidone, N-methyl-2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, heterocyclic compounds such as N-ethylmorpholine, sulfur-containing compounds such as sulfolane, dimethyl sulfoxide, 3-sulfolane, diacetone alcohol, polyfunctional compounds such as diethanolamine, and urea derivatives can be cited. Among them, polyols such as glycerol and diethylene glycol are more preferred.

[0277] Furthermore, the above anti-drying agents may be used alone or in combination of two or more.

[0278] These anti-drying agents are preferably contained in the ink for inkjet recording in an amount of 10% by mass to 50% by mass.

[0279] The ultraviolet absorber is used to improve the preservation of images.

[0280] As the ultraviolet absorber, benzotriazole compounds described in Japanese Patent Application Laid-Open Nos. 58-185677, 61-190537, 2-782, 5-197075, 9-34057, etc., benzophenone compounds described in Japanese Patent Application Laid-Open Nos. 46-2784, 5-194483, U.S. Patent No. 3214463, etc. can also be used. Compounds described in Japanese Patent Publication No. 48-30492, Japanese Patent Publication No. 56-21141, Japanese Patent Application Publication No. 10-88106, etc., triazine compounds described in Japanese Patent Application Publication No. 4-298503, Japanese Patent Application Publication No. 8-53427, Japanese Patent Application Publication No. 8-239368, Japanese Patent Application Publication No. 10-182621, Japanese Patent Application Publication No. 8-501291, etc., compounds described in Research Disclosure No. 24239, or compounds that absorb ultraviolet light and emit fluorescence, represented by stilbene-based and benzoxazole-based compounds, so-called fluorescent whitening agents.

[0281] The anti-fading agent is used for the purpose of improving the preservation of images.

[0282] As anti-fading agents, various organic and metal complex anti-fading agents can be used. As organic anti-fading agents, there are hydroquinones, alkoxyphenols, dialkoxyphenols, phenols, anilines, amines, indanes, chromans, alkoxyanilines, heterocyclics, etc., and as metal complexes, there are nickel complexes, zinc complexes, etc. More specifically, compounds included in items I to J in Section VII of Research Disclosure No. 17643, Research Disclosure No. 15162, the left column on page 650 of Research Disclosure No. 18716, page 527 of Research Disclosure No. 36544, page 872 of Research Disclosure No. 307105, compounds described in Japanese patents cited in Research Disclosure No. 15162, or compounds contained in the general formulas and compound examples of representative compounds described in JP-A-62-215272, pages 127 to 137, can be used.

[0283] Examples of the antifungal agent include sodium dehydroacetate, sodium benzoate, sodium pyrithione-1-oxide, ethyl p-hydroxybenzoate, 1,2-benzisothiazolin-3-one and its salts, etc. These are preferably contained in an amount of 0.02 to 1.00% by mass based on the total mass of the ink.

[0284] As the pH adjuster, a neutralizer (organic base, inorganic base) can be used. In order to improve the storage stability of the inkjet recording ink, the pH adjuster is preferably added so that the inkjet recording ink has a pH of 6 to 10, and more preferably 7 to 10.

[0285] As the surface tension adjusting agent, nonionic, cationic or anionic surfactants can be mentioned. In addition, the surface tension of the ink for inkjet recording is preferably 25mN / m to 70mN / m at 25°C, preferably 25mN / m to 60mN / m. In addition, the viscosity of the ink for inkjet recording is preferably 30mPa·s or less at 25°C. It is more preferably adjusted to 20mPa·s or less.

[0286] As examples of surfactants, preferred are anionic surfactants such as fatty acid salts, alkyl sulfate ester salts, alkylbenzene sulfonates, alkylnaphthalene sulfonates, dialkyl sulfosuccinates, alkyl phosphate ester salts, naphthalenesulfonic acid formalin condensates, polyoxyethylene alkyl sulfate ester salts, or 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, glycerol fatty acid esters, and oxyethyleneoxypropylene block copolymers. In addition, it is also preferred to use SURFYNOLS (manufactured by Air Products & Chemicals), which is an acetylene-based polyoxyethylene oxide surfactant. In addition, amine oxide-type amphoteric surfactants such as N, N-dimethyl-N-alkylamine oxides are also preferred. In addition, the substances listed as surfactants described in pp. (37) to (38) of Japanese Patent Application Laid-Open No. 59-157,636 and Research Disclosure No. 308119 (1989) can also be used.

[0287] As the defoaming agent, a fluorine-based compound, a silicone-based compound, a chelating agent represented by ethylenediaminetetraacetic acid (EDTA), or the like may be used as necessary.

[0288] When dispersing the compound represented by Formula 1, its tautomers and their salts in an aqueous medium, it is preferred that colored microparticles containing the compound and an oil-soluble polymer are dispersed in an aqueous medium as described in Japanese Patent Publication Nos. 11-286637, 2001-240763, 2001-262039, and 2001-247788, or that the compound represented by Formula 1, its tautomers and their salts dissolved in a high boiling point organic solvent are dispersed in an aqueous medium as described in Japanese Patent Publication Nos. 2001-262018, 2001-240763, 2001-335734, and 2002-80772. Regarding the specific method when the compound represented by Formula 1, its tautomer and its salt are dispersed in an aqueous medium, the oil-soluble polymer used, the high boiling point organic solvent, the additive and its usage, it is preferred to use those described in the above-mentioned Japanese Patent Gazette, etc. Alternatively, the compound represented by Formula 1, its tautomer and its salt can also be dispersed into a particulate state in a solid state. A dispersant or a surfactant can be used during dispersion. As a dispersing device, a simple agitator or impeller stirring method, an online stirring method, a grinding method (for example, a colloid mill, a ball mill, a sand mill, a grinder, a roller mill, a stirrer mill, etc.), an ultrasonic method, a high-pressure emulsification dispersion method (high-pressure homogenizer; as a specific commercially available device, there are Gaulin homogenizers, Microfluidizers, DeBEE2000, etc.) can be used. The method for preparing the inkjet recording ink is described in detail in the Japanese Patent Application Nos. 5-148436, 5-295312, 7-97541, 7-82515, 7-118584, 11-286637, and 2001-271003 in addition to the above-mentioned Japanese Patent Application, and can be used to prepare an inkjet recording ink containing the coloring composition of the present invention.

[0289] The aqueous medium may be a mixture containing water as a main component and, if necessary, a water-miscible organic solvent added thereto.

[0290] Examples of the water-miscible organic solvent include alcohols (e.g., methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, tert-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol), polyols (e.g., ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexylene glycol, pentylene glycol, glycerol, hexanetriol, 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, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate), The water-miscible organic solvents may be selected from the group consisting of monomethyl ether acetate, triethylene glycol monomethyl ether, triethylene glycol monoethyl ether, ethylene glycol monophenyl ether), amines (e.g., ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine) and other polar solvents (e.g., formamide, N,N-dimethylformamide, N,N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidinone, 1,3-dimethyl-2-imidazolidinone, acetonitrile, acetone). In addition, two or more of the water-miscible organic solvents may be used in combination.

[0291] When the coloring composition of the present invention is used as an inkjet recording ink, it preferably contains 0.2 to 10 parts by mass, more preferably 1 to 6 parts by mass, of the compound represented by Formula 1, its tautomer and a salt thereof, based on 100 parts by mass of the inkjet recording ink.

[0292] Furthermore, the ink for inkjet recording may use other pigments in combination. When two or more pigments are used in combination, the total content of the pigments is preferably within the above range.

[0293] (Dyeing method and dyed product)

[0294] The dyeing method according to the present invention is a dyeing method using the compound represented by Formula 1, its tautomer, or a salt thereof, and is preferably a dyeing method using the coloring composition according to the present invention.

[0295] The dyed material according to the present invention contains the compound represented by Formula 1, its tautomer or a salt thereof.

[0296] As a dyeing method using the compound represented by Formula 1, its tautomer or their salts, any method can be used as long as at least one selected from the compound represented by Formula 1, its tautomer and their salts is used as a dye, for example, methods such as dipping, kneading, coating, printing, inkjet printing, etc. can be used.

[0297] Furthermore, the dyeing method according to the present invention may use a known dyeing method in addition to the compound represented by Formula 1, its tautomer or a salt thereof.

[0298] The dyed product according to the present invention may contain a pigment and / or dye other than the compound represented by Formula 1, its tautomer or a salt thereof.

[0299] Furthermore, the dyeing part containing the compound represented by Formula 1, its tautomer or a salt thereof in the dyeing material according to the present invention may be a part of or the whole of the dyeing material.

[0300] As the dyed material in the dyed material involved in the present invention, natural fibers such as silk, kapok, and hemp; synthetic fibers such as nylon, polyester, acrylic acid, and polyurethane; inorganic materials such as glass, metal, and pottery; and papers such as ordinary paper, resin-coated paper, and special inkjet recording paper can be used.

[0301] Example

[0302] Hereinafter, the present invention will be described in detail by way of examples, but the present invention is not limited thereto. In the examples, "%" and "parts" represent "mass %" and "mass parts", respectively, unless otherwise specified.

[0303] (Example 1: Synthesis of Exemplary Compound M-2 and Exemplary Compound D-2)

[0304] [Chemical formula 35]

[0305]

[0306] 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. A solution of 2.3 g of sodium nitrite and 4 mL of water was added dropwise to the mixture, and after stirring for 1 hour, 4.9 mL of acetic acid was added to obtain a diazonium salt solution.

[0307] 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 the mixture was left as is for 4 days. 60 mL of water was added to the reaction mixture, and the precipitated crystals were filtered out and washed with water and methanol. The obtained crystals were dried to obtain 6.6 g of illustrative compound M-2.

[0308] 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)

[0309] 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 illustrative 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 below) for 1 hour, the precipitated crystals were filtered out and washed with water and methanol. The obtained crystals were stirred in 50 mL of acetonitrile, filtered out, washed with acetonitrile, and dried to obtain 4.5 g of illustrative compound D-2.

[0310] 1 H-NMR (CDCl3) δ = 15.0 (br., 1H), 7.51 (d, 1H), 7.31 (d, 1H), 6.56 (d, iH), 6.53 (d, 1H), 4.06 (s, 3H), 2.67 (s, 3H)

[0311] Maximum absorption wavelength (λmax): 492nm, molar absorption coefficient ε: 2.63×10 4 (N,N-dimethylformamide (DMF))

[0312] <Evaluation 1: Dyeing of inkjet paper by exemplary compound D-2>

[0313] Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.) 62 mg was added to 100 mL of pure water to prepare a surfactant solution. 2.5 g of the surfactant solution was added to a mixture of 250 mg of the exemplary compound D-2 and 2.5 mL of a 0.1 M (M = mol / L) sodium hydroxide aqueous solution and uniformly dissolved. Thus, a coloring composition containing the salt of the compound D-2 of the present invention was obtained.

[0314] The obtained coloring composition was applied to inkjet paper (manufactured by FUJIFILM Corporation) using a bar coater. A brown dyed product was obtained. The L of the obtained dyed product was measured using i1 Pro (manufactured by X-Rite Corporation). * 、a * and b * The results are shown in Table 1 below.

[0315] (Comparative Example 1: Dyeing of inkjet paper with Acid Brown M)

[0316] A coloring composition containing a salt of a comparative compound Acid Brown M was obtained in the same manner except that Acid Brown M was used instead of the above-mentioned exemplary compound D-2.

[0317] [Chemical formula 36]

[0318]

[0319] The obtained coloring composition was coated on inkjet paper painting (registered trademark, manufactured by FUJIFILM Corporation) using a rod coater. A reddish brown dyed product was obtained. The L of the obtained dyed product was measured using i1 Pro (manufactured by X-Rite Corporation). * 、a * and b * The results are shown in Table 1 below.

[0320] [Table 1]

[0321]

[0322] The compound column in Table 1 shows exemplary compounds used for evaluation of dyeing.

[0323] The compound according to the present invention, exemplified compound D-2, has a hue lower in chroma and lightness than the comparative compound Acid Brown M.

[0324] (Example 2: Synthesis of Exemplary Compound M-11 and Exemplary Compound D-11)

[0325] [Chemical formula 37]

[0326]

[0327] In a 200 mL three-necked flask, 14.7 g of 5-amino-3-methylthio-1,2,4-thiadiazole was dissolved in 80 mL of phosphoric acid (85%, manufactured by FUJIFILM Wako Pure Chemical Corporation), and the internal temperature was cooled to 0°C. While the internal temperature was maintained below 5°C, 6.9 g of sodium nitrite (manufactured by FUJIFILM Wako Pure Chemical Corporation) was slowly added thereto. After the addition was completed, the mixture was stirred at an internal temperature of 0°C to 5°C for 1 hour to prepare a diazonium salt solution.

[0328] In another 500mL three-necked flask, 12.6g of 1,3,5-benzenetriol (manufactured by FUJIFILM Wako PureChemical Corporation) was dissolved in 200mL of methanol and the internal temperature was cooled to 5°C. While maintaining the internal temperature below 10°C, the newly prepared diazonium salt solution was slowly added thereto. After the addition was completed, the mixture was stirred at an internal temperature of 0 to 5°C for 30 minutes, and then stirred at 25°C for 1 hour. The precipitated crystals were filtered, washed three times with 200mL of methanol, and dried in a 50°C air-blown dryer for 6 hours to obtain powder crystals of the exemplary compound M-11. Yield: 25.6g (yield: 90%)

[0329] 1 H-NMR (DMSO-d6) δ = 12.71 (br., 2H), 5.96 (s, 2H), 2.64 (s, 3H)

[0330] In a 200 mL three-necked flask, 9.8 g of 5-amino-1-methylpyrazole phosphate was dissolved in 80 mL of phosphoric acid (85%, manufactured by FUJIFILM Wako Pure Chemical Corporation), and the internal temperature was cooled to 0°C. While maintaining the internal temperature below 5°C, 3.5 g of sodium nitrite (manufactured by FUJIFILM Wako Pure Chemical Corporation) was slowly added thereto. After the addition was completed, the mixture was stirred at an internal temperature of 0°C to 5°C for 1 hour to prepare a diazonium salt solution.

[0331] In another 500mL three-necked flask, 14.2g of the exemplary compound M-11 was suspended and dispersed in 200mL of methanol, and the internal temperature was cooled to 5°C. While maintaining the internal temperature below 10°C, the newly prepared diazonium salt solution was slowly added thereto. After the addition was completed, 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 filtered and washed three times with 200mL of methanol. The crystals were heated and suspended and washed with 100mL of acetonitrile at 50°C, and dried in a 50°C air-blown dryer for 6 hours to obtain green glossy crystals of the exemplary compound D-11. Yield 16.2g (yield 83%)

[0332] 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)

[0333] λmax:424nm,ε:2.44×10 4 (DMF)

[0334] The hue of the exemplary compound D-11 was low in chroma and lightness.

[0335] (Example 3: Synthesis of Exemplary Compound N-100)

[0336] [Chemical formula 38]

[0337]

[0338] 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 below), a 5% aqueous sodium bicarbonate solution was added under ice-cooling to pH 7, the precipitated crystals were filtered out, and washed with water. The obtained crystals were dried to obtain 9.8 g of the exemplary compound N-100.

[0339] 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).

[0340] The spectral characteristics in N, N-dimethylformamide are: λmax: 470nm, molar absorption coefficient ε: 4.00×10 4 .

[0341] 3-Hydroxy-N,N-dimethylaniline has three reaction sites that can initiate the diazo coupling reaction, and selectively obtains the exemplary compound N-100. As shown below, the exemplary compound N-100 serves as a valuable synthetic intermediate for obtaining the exemplary compounds N-1, N-2, and N-6.

[0342] (Example 4: Synthesis of Exemplary Compound N-1)

[0343] [Chemical formula 39]

[0344]

[0345] 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 for 1 hour at room temperature (20°C to 25°C, the same below), a 5% aqueous sodium bicarbonate solution was added under ice-cooling to pH 7, and the precipitated crystals were filtered out and washed with water. The obtained crystals were dried and purified by silica gel chromatography to obtain 2.0 g of the exemplary compound N-1.

[0346] 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).

[0347] The spectral characteristics in N, N-dimethylformamide are: λmax1: 521nm, molar absorption coefficient ε: 2.03×10 4 , λmax2: 442nm, molar absorption coefficient ε: 2.13×10 4 , λmax3: 347nm, molar absorption coefficient ε: 2.13×10 4 .

[0348] (Example 5: Synthesis of Exemplary Compound N-2 and Exemplary Compound N-6)

[0349] [Chemical formula 40]

[0350]

[0351] 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 stirring for 30 minutes, 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 for 1 hour at room temperature (20°C to 25°C, the same below), a 5% aqueous sodium bicarbonate solution was added under ice-cooling to pH 7, and the precipitated crystals were filtered out 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.

[0352] ( 1 H-NMR (CDCl3)

[0353] Exemplary compound N-2:

[0354] 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)

[0355] Exemplary compound N-6:

[0356] 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)

[0357] (Spectral characteristics in N,N-dimethylformamide)

[0358] Exemplary compound N-1:

[0359] λmax1: 521nm, molar absorption coefficient ε: 2.03×10 4

[0360] λmax2: 442nm, molar absorption coefficient ε: 2.13×10 4

[0361] λmax3: 347nm, molar absorption coefficient ε: 2.13×10 4

[0362] Exemplary compound N-2:

[0363] λmax1: 600nm, molar absorption coefficient ε: 1.70×10 4

[0364] λmax2: 496nm, molar absorption coefficient ε: 2.13×10 4

[0365] λmax3: 419nm, molar absorption coefficient ε: 2.70×10 4

[0366] Exemplary compound N-6:

[0367] λmax1: 449nm, molar absorption coefficient ε: 3.45×10 4

[0368] λmax2: 420nm, molar absorption coefficient ε: 3.35×10 4

[0369] <Evaluation 2: Dyeing of inkjet paper by exemplary compound N-1, N-2 or N-6>

[0370] (1) Preparation of a Coloring Composition Containing a Salt of Exemplary Compound N-1>

[0371] Surfynol 465 (manufactured by Nissin Chemical Industry Co., Ltd.) 62 mg was added to 100 mL of pure water to prepare a surfactant solution. 2.5 g of the surfactant solution was added to a mixture of 47 mg of the exemplary compound N-1 and 2.5 mL of a 0.1 M (M = mol / L) sodium hydroxide aqueous solution and uniformly dissolved. Thus, a coloring composition containing the salt of the compound of the present invention, ie, the exemplary compound N-1, was obtained.

[0372] (2) Preparation of a Coloring Composition Containing a Salt of Exemplary Compound N-2

[0373] A coloring composition containing a salt of the compound of the present invention, ie, the salt of the exemplary compound N-2, was obtained in the same manner except that 61 mg of the exemplary compound N-2 was used instead of the exemplary compound N-1.

[0374] (3) Preparation of a Coloring Composition Containing a Salt of Exemplary Compound N-6>

[0375] A coloring composition containing a salt of the compound of the present invention, ie, the salt of the exemplary compound N-6, was obtained in the same manner except that 47 mg of the exemplary compound N-6 was used instead of the exemplary compound N-1.

[0376] Each coloring composition obtained above was applied to inkjet paper (manufactured by FUJIFILM Corporation) using a bar coater. A brown dyed product was obtained. The L of the obtained dyed product was measured using i1 Pro (manufactured by X-Rite Corporation). * 、a * and b * .

[0377] The above evaluation results are shown in the following Table 2. Table 2 also shows the evaluation results of Comparative Example 1.

[0378] [Table 2]

[0379]

[0380] The compound column in Table 2 shows exemplary compounds used for evaluating the coloring composition.

[0381] The compounds according to the present invention, ie, the exemplary compounds N-1, N-2 and N-6, have hues lower in chroma and lightness than the comparative compound Acid Brown M.

[0382] 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 described in this specification are incorporated herein by reference to the same extent as if each document, patent application, or technical standard was specifically and individually described as being incorporated by reference.

Claims

1. A compound represented by the following formula 1, its tautomer or a salt thereof, In formula 1, X- represents R 2a R 2b N-, R 2a and R 2b Each independently represents a hydrogen atom or an alkyl group, R 2a and R 2b Same or different, R 2a With R 2b are optionally bonded to form a nitrogen-containing heterocyclic ring, R each independently represents a substituent, n represents 0, Ar represents an aromatic hydrocarbon group or a heterocyclic group, m1 represents 2 or 3, Ar is the same or different, wherein, Ar is a group represented by any of the following formulae (A-1) to (A-7), (A-9) to (A-25), (A-27), and (A-28), (A-2) (A-19) In formula (A-1) to (A-7), formula (A-9) to (A-25), formula (A-27), and formula (A-28), * indicates the position of bonding to the azo group in formula 1, and R 21 ~R 27 , R 31 , R 33 ~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 hydroxyl 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, and 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 hydroxyl 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, and R 21 ~R 28 , R 31 ~R 50 , R 52 and R 53 The adjacent groups in the molecule are optionally bonded to each other to form a saturated or unsaturated 5-membered ring 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, i, j, k, l and o represent integers of 0 to 2, m represents 0 or 1, and R in the same molecule is 1 or 2. 21 ~R 28 , R 31 ~R 50 , R 52 and R 53 Two or more groups represented are the same or different from each other.

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

3. The compound according to claim 1 or 2, its tautomer or a salt thereof, wherein: The bonding position of X- is meta relative to the hydroxyl group. 4 . The compound according to claim 1 or 2 , its tautomer or a salt thereof, which is a disazo dye. 5 . A coloring composition comprising the compound according to claim 1 , its tautomer or a salt thereof. The coloring composition according to claim 5 , further comprising an aqueous solvent.

7. A dyeing method using the coloring composition according to claim 5 or 6. 8 . A dyed material comprising the compound according to claim 1 , its tautomer or a salt thereof.

9. A method for producing a compound according to any one of claims 1 to 4, a tautomer thereof or a salt thereof, comprising the 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', In Formula 5', Formula 6 and Formula 7', Ar 11 represents a heterocyclic group, R represents a substituent, and X- represents R 2a R 2b N-, R 2a and R 2b Each independently represents a hydrogen atom or an alkyl group, and n represents 0.

10. A method for producing the compound according to any one of claims 1 to 4, its tautomer or its salt, comprising the following steps: 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, In Formula 5 to Formula 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 2a R 2b N-, R 2a and R 2b Each independently represents a hydrogen atom or an alkyl group, and n represents 0, wherein, Ar 1 and Ar 2 They are not aromatic hydrocarbon groups at the same time.

11. A method for producing the compound according to any one of claims 1 to 4, its tautomer or its salt, comprising the following steps: 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 the formula 14 with a diazonium salt represented by the following formula 8 to obtain a compound represented by the following formula 15, 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, R 2a and R 2b Each independently represents a hydrogen atom or an alkyl group, R 2a and R 2b Same or different, R 2a With R 2b are optionally bonded to form a nitrogen-containing heterocyclic ring, R represents a substituent, n1 represents 0, wherein, Ar 1 and Ar 2 They are not aromatic hydrocarbon groups at the same time.

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