JP2009073978A - Method for producing azo pigment and azo pigment - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an azo pigment, which is excellent in color characteristics such as coloring power and hue and in durability such as lightfastness and ozone resistance, with good reproducibility and high efficiency. <P>SOLUTION: The azo pigment represented by a formula (1) is produced by carrying out a coupling reaction between a diazonium compound with heterocyclic amine modified into diazonium and an intermediate compound of the object azo pigment in the presence of sulfuric acid. In the formula (1), Het is an aromatic heterocyclic ring such as a 5-amino-3-methyl-1,2,4-thiazolyl, and G is an atomic group constituting a 5-6 member heterocyclic ring. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a method for producing an azo pigment and an azo pigment.

  In recent years, a material for forming a color image has been mainly used as an image recording material, and specifically, an ink jet recording material, a thermal transfer recording material, an electrophotographic recording material, a transfer halogen. Silver halide photosensitive materials, printing inks, recording pens, and the like are actively used. Further, a color filter is used for recording and reproducing a color image on an image pickup device such as a CCD in a photographing apparatus and on an LCD or PDP in a display. In these color image recording materials and color filters, three primary colors (dyes and pigments) of the so-called additive color mixture method and subtractive color mixture method are used to display or record full color images. In fact, there is no fast-acting dye that has absorption characteristics that can realize the above-mentioned conditions and can withstand various use conditions and environmental conditions, and improvement is strongly desired.

The dyes and pigments used in each of the above applications must have the following properties in common. That is, it has preferable absorption characteristics in terms of color reproducibility, fastness under environmental conditions to be used, for example, light resistance, heat resistance, good resistance to oxidizing gases such as ozone, and the like. In addition, when the pigment is a pigment, it is substantially insoluble in water and organic solvents and has good chemical fastness, and even when used as particles, the preferred absorption characteristics in the molecular dispersion state are impaired. It is also necessary to have properties such as absence. The required characteristics can be controlled by the strength of intermolecular interaction, but they are in a trade-off relationship and are difficult to achieve at the same time.
In addition, when using the pigment, in addition to having a particle size and a particle shape necessary for expressing the desired transparency, fastness under the environmental conditions used, such as light resistance, heat resistance, Good resistance to oxidative gases such as ozone, and other chemical fastness to organic solvents and sulfurous acid gas. Disperse even fine particles in the medium used, and stable dispersion. , Etc. are also required. In particular, there is a strong demand for pigments that have a good yellow hue, have high coloring power among light, wet heat, and active gases in the environment, and are fast to light.

  That is, the required performance for pigments is more diverse than dyes that require performance as pigment molecules, and not only the performance as pigment molecules but also the above requirements as solids (fine particle dispersions) as aggregates of pigment molecules All performance needs to be satisfied. In particular, control of crystal polymorphism is indispensable in order to keep the performance and quality of pigments constant. For example, in phthalocyanine pigments and quinacridone pigments, many patent applications relating to production methods for controlling crystal polymorphism have been made. (For example, see Patent Documents 1 to 3).

  Azo pigments are widely used in printing inks, ink-jet inks, electrophotographic materials, and the like because they are excellent in hue and coloring power, which are color characteristics. Of these, the most typically used yellow azo pigments are diarylide pigments. Examples of diarylide pigments include C.I. I. Pigment Yellow 12, 13 and 17 and the like. However, since diarylide pigments are very inferior in fastness, especially light resistance, when the printed matter is exposed to light, the pigment is decomposed and discolored, which is not suitable for long-term storage of the printed matter.

  In order to improve such a defect, an azo pigment having improved fastness by increasing the molecular weight or introducing a group having a strong intermolecular interaction is also disclosed (for example, Patent Documents 4 to 4). 6). However, even in the improved pigment, for example, the pigment described in Patent Document 1 has improved light resistance, but is still insufficient. For example, the pigment described in Patent Documents 2 and 3 has a green hue. There was a drawback that coloring power was lowered by taste and color characteristics were inferior.

  Patent Document 7 discloses a dye having absorption characteristics excellent in color reproducibility and sufficient fastness. However, since all of the specific compounds described in the patent document are dissolved in water or an organic solvent, the chemical fastness is not sufficient.

Therefore, there is a demand for an azo pigment that has excellent color characteristics such as coloring power and hue, and excellent durability such as light resistance and ozone resistance. However, since the azo pigment exhibits different structural isomerism and crystal polymorphism depending on the production method, it is difficult to produce the azo pigment having the structural isomerism and crystal polymorphism exhibiting desired characteristics with high reproducibility and high purity. Met.
JP 2003-160738 A JP 2007-9007 A Japanese Patent Laid-Open No. 11-53767 JP-A-56-38354 U.S. Pat. No. 2,936,306 Japanese Patent Laid-Open No. 11-1000051 JP 2003-277661 A

  The present invention is highly reproducible while controlling azo pigments having excellent color characteristics such as tinting strength and hue, and excellent durability such as light resistance and ozone resistance to specific structural isomerism and crystal polymorphism. It aims at providing the manufacturing method which can manufacture efficiently.

  As a result of intensive studies in view of the above-mentioned circumstances, the present inventors have produced azo pigments with high reproducibility and high efficiency while controlling the structural isomerism and crystal polymorphism of azo compounds by coupling in the presence of sulfuric acid. As a result, the present invention was completed.

That is, the present invention is as follows.
[1]
An azo pigment represented by the following general formula (4) by a coupling reaction between a diazonium compound obtained by diazonium-izing a heterocyclic amine represented by the following general formula (1) and a compound represented by the following general formula (3) A process for producing an azo pigment represented by the following general formula (4), wherein a coupling reaction is carried out in the presence of sulfuric acid.
General formula (1):
Het-NH ₂
(In general formula (1), Het represents a group selected from the group of aromatic heterocyclic groups represented by the following general formula (2). * Represents a binding site with an amino group in general formula (1). .)
General formula (2):

(In General Formula (2), X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ each independently represent a hydrogen atom or a substituent.)
General formula (3):

(In General Formula (3), R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. G represents an atomic group capable of constituting a 5- to 6-membered heterocycle. W represents G. And represents a substituent that can be bonded to the heterocycle, s represents an integer of 1 to 4, t represents an integer of 0 to 3, and s + t is an integer of 4 or less.)
General formula (4):

(In General Formula (4), R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. G represents an atomic group capable of constituting a 5- to 6-membered heterocycle. W represents G. Represents a substituent that can be bonded to a heterocyclic ring, s represents an integer of 1 to 4, t represents an integer of 0 to 3, and s + t is an integer of 4 or less, Het-1 and Het-2 are independent of each other. Represents a group selected from the group of aromatic heterocyclic groups represented by the general formula (2), and * represents a bonding site with an azo group in the general formula (4).
[2]
[1] The production method according to [1], wherein the heterocyclic amine represented by the general formula (1) is diazoniumized using nitrosylsulfuric acid.
[3]
The method according to [1] or [2], wherein the heterocyclic amine represented by the general formula (1) is a compound represented by the following general formula (5).
General formula (5):

(In general formula (5), Y represents a hydrogen atom or a substituent.)
[4]
The production method according to any one of [1] to [3], wherein the azo pigment represented by the general formula (4) is an azo pigment represented by the following general formula (6).
General formula (6):

(In General Formula (6), R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. Het-1 and Het-2 each independently represent an aromatic heterocycle represented by General Formula (2). Represents a group selected from the group of ring groups, * represents a bonding site with an azo group in the general formula (6).
[5]
An azo pigment represented by the general formula (4), a salt or a hydrate thereof, which is produced by the production method according to any one of [1] to [4].
[6]
[5] A colorant composition comprising at least one azo pigment, salt or hydrate thereof according to [5].

  According to the present invention, an azo pigment having excellent color characteristics such as tinting strength and hue, and excellent durability such as light resistance and ozone resistance is controlled with specific structural isomerism and crystal polymorphism with good reproducibility. A production method capable of producing with high efficiency is provided. By dispersing the pigment produced according to the present invention in various media, for example, ink for printing such as ink jet, which is excellent in color characteristics, durability and dispersion stability, color toner for electrophotography, LCD, PDP, etc. It can be used for color filters, paints, colored plastics, etc. used in image sensors such as displays and CCDs.

Hereinafter, the present invention will be described in detail.
Here, Hammett's substituent constant σp value used in the present specification will be described briefly.
Hammett's rule is a method for determining the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Areas of Chemistry” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it is limited only to a substituent having a known value that can be found in the above-mentioned book. However, it goes without saying that even if the value is unknown, it also includes a substituent that would be included in the range when measured based on Hammett's rule. Although the compounds represented by the general formulas (1) to (6) of the present invention are not benzene derivatives, the σp value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value will be used in this sense.

[Azo pigment]
The azo pigment produced in the present invention is represented by the general formula (4).

Hereinafter, the azo pigment represented by the general formula (4) will be described in detail. The azo pigment may be a salt or hydrate thereof.
General formula (4)

(In general formula (1), R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. G represents an atomic group capable of constituting a 5- to 6-membered heterocycle. S represents an integer of 1 to 4, t represents an integer of 0 to 3, and s + t is an integer of 4 or less, and Het-1 and Het-2 are respectively Independently, it represents a group selected from the group of aromatic heterocyclic groups represented by the following general formula (2) (* represents a bonding site with an azo group in the general formula (4)).
General formula (2)

(In General Formula (2), X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ each independently represent a hydrogen atom or a substituent.)

Hereinafter, the general formula (4) will be described in more detail.
In the general formula (4), the heterocyclic group represented by Het-1 or Het-2 represents a group selected from the group of aromatic heterocyclic groups represented by the general formula (2). The substituents on the heterocycle may be bonded to each other to form a condensed ring. * Represents a binding site with the azo group in the general formula (4).

  Examples of the heterocyclic group include (1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11 ) Is preferable, and (2), (5), (6), (7), (8), (9), and (10) are preferable, and (2), (5), (6), (7) are particularly preferable. ) And (10) are preferable, and (7) is the most preferable among them.

In the general formula (2), X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ each independently represent a hydrogen atom or a substituent.

Examples of the substituent represented by X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ include a linear or branched alkyl group having 1 to 12 carbon atoms and a straight chain having 7 to 18 carbon atoms. A chain or branched aralkyl group, a linear or branched alkenyl group having 2 to 12 carbon atoms, a linear or branched alkynyl group having 2 to 12 carbon atoms, a linear or branched cycloalkyl group having 3 to 12 carbon atoms, A linear or branched cycloalkenyl group having 3 to 12 carbon atoms. (For example, methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, sec-butyl, t-butyl, 2-ethylhexyl, 2-methylsulfonylethyl, 3-phenoxypropyl, trifluoromethyl, cyclopentyl) , Halogen atoms (eg, chlorine atom, bromine atom), aryl groups (eg, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl), heterocyclic groups (eg, imidazolyl, pyrazolyl, triazolyl) 2-furyl, 2-thienyl, 2-pyrimidinyl, 2-benzothiazolyl), cyano group, hydroxyl group, nitro group, carboxy group, amino group, alkyloxy group (for example, methoxy, ethoxy, 2-methoxyethoxy, 2- Methylsulfonylethoxy), aryloxy groups (for example, phenoxy, 2-methylphenyl) Noxy, 4-t-butylphenoxy, 3-nitrophenoxy, 3-t-butyloxycarbonylphenoxy, 3-methoxycarbonylphenyloxy, acylamino groups (for example, acetamide, benzamide, 4- (3-t-butyl-4- Hydroxyphenoxy) butanamide), alkylamino groups (eg methylamino, butylamino, diethylamino, methylbutylamino), arylamino groups (eg phenylamino, 2-chloroanilino), ureido groups (eg phenylureido, methylureido, N, N-dibutylureido), sulfamoylamino group (for example, N, N-dipropylsulfamoylamino), alkylthio group (for example, methylthio, octylthio, 2-phenoxyethylthio), arylthio group (for example, Phenylthio, 2-butoxy-5-t-octylphenylthio, 2-carboxyphenylthio), alkyloxycarbonylamino groups (eg methoxycarbonylamino), alkylsulfonylamino groups and arylsulfonylamino groups (eg methylsulfonylamino, Phenylsulfonylamino, p-toluenesulfonylamino), carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl), N-phenylsulfamoyl), sulfonyl groups (eg, methylsulfonyl, octylsulfonyl, phenylsulfonyl, p-toluenesulfonyl), alkyloxycarbonyl groups (eg, methoxycarbonyl, Tiloxycarbonyl), heterocyclic oxy groups (eg 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy), azo groups (eg phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo) 2-hydroxy-4-propanoylphenylazo), acyloxy group (for example, acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethyl) Silyloxy), aryloxycarbonylamino group (eg, phenoxycarbonylamino), imide group (eg, N-succinimide, N-phthalimide), heterocyclic thio group (eg, 2-benzothiazolylthio, 2,4-dithio) -Fe Xy-1,3,5-triazole-6-thio, 2-pyridylthio), sulfinyl group (for example, 3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), An aryloxycarbonyl group (for example, phenoxycarbonyl), an acyl group (for example, acetyl, 3-phenylpropanoyl, benzoyl), an ionic hydrophilic group (for example, a carboxyl group, a sulfo group, a phosphono group, and a quaternary ammonium group). Can be mentioned.

In the general formula (2), preferable examples of substituents for X and W ₀ are each independently an electron-withdrawing group. In particular, it is an electron-withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, and more preferably an electron-withdrawing group having a σp value of 0.30 or more. The upper limit is 1.0 or less electron withdrawing group.

  Specific examples of X which is an electron-withdrawing group having a σp value of 0.20 or more include an acyl group, an acyloxy group, a carbamoyl group, an alkyloxycarbonyl group, an aryloxycarbonyl group, a cyano group, a nitro group, and a dialkylphosphono group Diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, halogenated alkyl group, A halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with another electron-withdrawing group having a σp value of 0.20 or more, a heterocyclic group, a halogen atom, Azo group or selenocyane Group.

Preferable examples of X and W ₀ are each independently an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, and an alkyloxycarbonyl group having 2 to 12 carbon atoms. An aryloxycarbonyl group having 7 to 18 carbon atoms, a cyano group, a nitro group, an alkylsulfinyl group having 1 to 12 carbon atoms, an arylsulfinyl group having 6 to 18 carbon atoms, an alkylsulfonyl group having 1 to 12 carbon atoms, and a carbon number An arylsulfonyl group having 6 to 18 carbon atoms, a sulfamoyl group having 0 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, a halogenated alkyloxy group having 1 to 12 carbon atoms, and a halogenated alkylthio group having 1 to 12 carbon atoms , A halogenated aryloxy group having 7 to 18 carbon atoms, 7 carbon atoms substituted with 2 or more other electron-withdrawing groups having σp of 0.20 or more 18 aryl group, and a nitrogen atom, an oxygen atom or 5-8 membered ring having sulfur atom include a heterocyclic group having 1 to 18 carbon atoms.

  More preferably, they are a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms. Particularly preferred are a cyano group, an alkylsulfonyl group having 1 to 8 carbon atoms, an arylsulfonyl group having 6 to 12 carbon atoms, or a sulfamoyl group having 0 to 8 carbon atoms, among which a cyano group, a methanesulfonyl group, a phenyl group A sulfonyl group and a sulfamoyl group are preferable, a cyano group and a methanesulfonyl group are more preferable, and a cyano group is most preferable.

In the general formula (2), preferred examples of Z include a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, substituted Or an unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or an acyl group; Particularly preferred substituents are a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or an acyl group. The substituent is preferably a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group. Examples of the substituent group, _X in the general formula _{(2), Y, Z,} W 0, W 1, W 2, W 3, W can be the same as the substituents exemplified in _4.

In formula (2), preferred examples of Y and W _{1 to} W ₄ are independently a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, and a substituted or unsubstituted total carbon number of C6 to C6. A C18 aryl group, or a substituted or unsubstituted C4-C12 heterocyclic group having a total carbon number is preferable, and among them, a hydrogen atom, a linear alkyl group having a total carbon number of C1-C8 and / or a branched alkyl group are preferable. In particular, a hydrogen atom or a C1-C8 alkyl group is preferable, and a hydrogen atom is most preferable.

In the general formula (4), preferred examples of R ₁ , R ₂ and W will be described in detail.

R ₁ , R ₂ and W each independently represent a hydrogen atom or a substituent.
When R ₁ , R ₂ and W each represent a monovalent substituent, examples of the monovalent substituent are each independently a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, Aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino Group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonylamino group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, aryl Sulfonylamino group, alkyl Thio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group, phosphinyl group Phosphinyloxy group, phosphinylamino group, silyl group, azo group, imide group and phosphoryl group, each of which may further have a substituent.

Among these, particularly preferred R ₁ , R ₂ and W are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, alkoxy group, amide group, ureido group, alkylsulfonylamino group. , Arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, or alkoxycarbonyl group, particularly hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, hydroxyl group, alkylsulfonyl group, An arylsulfonyl group, a heterocyclic group or an alkoxycarbonyl group is preferable, and a hydrogen atom, an alkyl group, an aryl group, a hydroxyl group or an alkoxycarbonyl group is most preferable.

Hereinafter, R ₁ , R ₂ and W will be described in more detail.
The halogen atom represented by R ₁ , R ₂ and W represents a chlorine atom, a bromine atom or an iodine atom. Of these, a chlorine atom or a bromine atom is preferable, and a chlorine atom is particularly preferable.

The alkyl group represented by R ₁ , R ₂ and W includes a substituted or unsubstituted alkyl group. The substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 30 carbon atoms. Examples of the substituent group, _X in the general formula _{(2), Y, Z,} W 0, W 1, W 2, W 3, W can be the same as the substituents exemplified in _4. Of these, a hydroxy group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (may be in a salt form) or a carboxyl group (may be in a salt form) is preferable. Examples of the alkyl group include methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, s-butyl, t-butyl, n-octyl, eicosyl, 2-chloroethyl, hydroxyethyl, cyanoethyl. Or 4-sulfobutyl can be mentioned.

The cycloalkyl group represented by R ₁ , R ₂ and W includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 5 to 30 carbon atoms. Examples of the substituent group, _X in the general formula _{(2), Y, Z,} W 0, W 1, W 2, W 3, W can be the same as the substituents exemplified in _4. Examples of the cycloalkyl group may include cyclohexyl, cyclopentyl, or 4-n-dodecylcyclohexyl.

The aralkyl group represented by R ₁ , R ₂ and W includes a substituted or unsubstituted aralkyl group. As the substituted or unsubstituted aralkyl group, an aralkyl group having 7 to 30 carbon atoms is preferable. Examples of the substituent group, _X in the general formula _{(2), Y, Z,} W 0, W 1, W 2, W 3, W can be the same as the substituents exemplified in _4. Examples of the aralkyl include benzyl and 2-phenethyl.

The alkenyl group represented by R ₁ , R ₂ and W represents a linear, branched or cyclic substituted or unsubstituted alkenyl group. Preferred examples include C2-C30 substituted or unsubstituted alkenyl groups such as vinyl, allyl, prenyl, geranyl, oleyl, 2-cyclopenten-1-yl, 2-cyclohexen-1-yl and the like.

The alkynyl group represented by R ₁ , R ₂ and W is a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms, and examples thereof include ethynyl and propargyl.

The aryl group represented by R ₁ , R ₂ and W is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, or o-hexadecanoylaminophenyl. It is. Examples of the substituent group, _X in the general formula _{(2), Y, Z,} W 0, W 1, W 2, W 3, W can be the same as the substituents exemplified in _4.

The heterocyclic group represented by R ₁ , R ₂ and W is a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound. Yes, they may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. Examples of the substituent group, _X in the general formula _{(2), Y, Z,} W 0, W 1, W 2, W 3, W can be the same as the substituents exemplified in _4. Examples of the heterocyclic group include, but are not limited to, substitution positions: pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene Benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. Can be mentioned.

The alkoxy group represented by R ₁ , R ₂ and W includes a substituted or unsubstituted alkoxy group. As the substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. Examples of the substituent group, _X in the general formula _{(2), Y, Z,} W 0, W 1, W 2, W 3, W can be the same as the substituents exemplified in _4. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

The aryloxy group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the substituent group, _X in the general formula _{(2), Y, Z,} W 0, W 1, W 2, W 3, W can be the same as the substituents exemplified in _4. Examples of the aryloxy group include phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy and the like.

The silyloxy group represented by R ₁ , R ₂ and W is preferably a silyloxy group having 3 to 20 carbon atoms, and examples thereof include trimethylsilyloxy and t-butyldimethylsilyloxy.

The heterocyclic oxy group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. Examples of the substituent group, _X in the general formula _{(2), Y, Z,} W 0, W 1, W 2, W 3, W can be the same as the substituents exemplified in _4. Examples of the heterocyclic oxy group include 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy and the like.

The acyloxy group represented by R ₁ , R ₂ and W is a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, and a substituted or unsubstituted arylcarbonyloxy group having 6 to 30 carbon atoms. Are preferable, and examples of the substituent include the same substituents as those described for X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ in the general formula (2). . Examples of the acyloxy group include formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy and the like.

The carbamoyloxy group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. Examples of the substituent include X and Y in the general formula (2). , Z, W ₀ , W ₁ , W ₂ , W ₃ , W ₄ and the same substituents as mentioned above can be mentioned. Examples of the carbamoyloxy group include, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyl. Examples include oxy.

The alkoxycarbonyloxy group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms. Examples of the substituent include X in the general formula (2), _{Y, Z, W 0, W} 1, W 2, W 3, W can be the same as the substituents exemplified in _4. Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy and the like.

The aryloxycarbonyloxy group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. mention may be made of _{X, Y, Z,} and _{W 0, W 1, W 2} , W 3, same as the substituents exemplified in _{W 4} in the formula (2). Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy and the like.

The amino group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. the embodiments, _X in the formula _{(2), Y, Z,} W 0, W 1, W 2, W 3, W can be the same as the substituents exemplified in _4. Examples of the amino group include, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, hydroxyethylamino, carboxyethylamino, sulfoethylamino, 3,5-dicarboxyanilino And so on.

The acylamino group represented by R ₁ , R ₂ and W is a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms. Are preferable, and examples of the substituent include the same substituents as those described for X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ in the general formula (2). . Examples of the acylamino group include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino, and the like.

The aminocarbonylamino group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. Examples of the substituent include X in the general formula (2). , Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , W ₄ and the same substituents as mentioned above can be exemplified. Examples of the aminocarbonylamino group include carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino and the like.

The alkoxycarbonylamino group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. Examples of the substituent include X in the general formula (2), _{Y, Z, W 0, W} 1, W 2, W 3, W can be the same as the substituents exemplified in _4. Examples of the alkoxycarbonylamino group include methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino and the like.

The aryloxycarbonylamino group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. Examples of the substituent include the above general formula (2) And the same substituents as mentioned for X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ . Examples of the aryloxycarbonylamino group include phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino and the like.

The sulfamoylamino group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. Examples of the substituent include the above general formula (2) And the same substituents as mentioned for X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ . Examples of the sulfamoylamino group include sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino and the like.

The alkyl and arylsulfonylamino groups represented by R ₁ , R ₂ and W are substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, substituted or unsubstituted arylsulfonylamino groups having 6 to 30 carbon atoms Are preferable, and examples of the substituent include the same substituents as those described for X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ in the general formula (2). . Examples of the alkylsulfonylamino group and arylsulfonylamino group include, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino and the like. I can do it.

The alkylthio group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. Examples of the substituent include X, Y and Z in the general formula (2). , W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ can be exemplified by the same substituents. Examples of the alkylthio group include methylthio, ethylthio, n-hexadecylthio and the like.

The arylthio group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms. Examples of the substituent include X, Y, Z, and the like in the general formula (2). _{W 0, W 1, W 2} , W 3, W can be the same as the substituents exemplified in _4. Examples of the arylthio group include phenylthio, p-chlorophenylthio, m-methoxyphenylthio and the like.

The heterocyclic thio group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. Examples of the substituent include X in the general formula (2). , Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , W ₄ and the same substituents as mentioned above can be exemplified. Examples of the heterocyclic thio group include 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio and the like.

The sulfamoyl group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. Examples of the substituent include X, Y and Z in the general formula (2). , W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ can be exemplified by the same substituents. Examples of the sulfamoyl group include, for example, N-ethylsulfamoyl, N- (3-dodecyloxypropyl) sulfamoyl, N, N-dimethylsulfamoyl, N-acetylsulfamoyl, N-benzoylsulfamoyl. N- (N′-phenylcarbamoyl) sulfamoyl) and the like.

The alkyl and arylsulfinyl groups represented by R ₁ , R ₂ and W are preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms and a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms. As examples of the above, the same substituents as those exemplified in X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ and W ₄ in the general formula (2) can be mentioned. Examples of the alkyl and arylsulfinyl groups include methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl and the like.

The alkyl and arylsulfonyl groups represented by R ₁ , R ₂ and W are preferably substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms, and substituted or unsubstituted arylsulfonyl groups having 6 to 30 carbon atoms. As examples of the above, the same substituents as those exemplified in X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ and W ₄ in the general formula (2) can be mentioned. Examples of the alkyl and arylsulfonyl groups include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl and the like.

The acyl group represented by R ₁ , R ₂ and W is a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, carbon number A heterocyclic carbonyl group bonded to a carbonyl group with 4 to 30 substituted or unsubstituted carbon atoms is preferable. Examples of the substituent include X, Y, Z, W ₀ and W in the general formula (2). Examples thereof include the same substituents as mentioned for ₁ , W ₂ , W ₃ and W ₄ . Examples of the acyl group include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl and the like.

The aryloxycarbonyl group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. Examples of the substituent include X in the general formula (2). , Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , W ₄ and the same substituents as mentioned above can be exemplified. Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl, and the like.

The alkoxycarbonyl group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. Examples of the substituent include X, Y, and _{Z, W 0, W 1,} W 2, W 3, W can be the same as the substituents exemplified in _4. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and the like.

The carbamoyl group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. Examples of the substituent include X, Y, Z in the general formula (2). , W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ can be exemplified by the same substituents. Examples of the carbamoyl group include carbamoyl, N-methylcarbamoyl, N, N-dimethylcarbamoyl, N, N-di-n-octylcarbamoyl, N- (methylsulfonyl) carbamoyl and the like.

The phosphino group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms. Examples of the substituent include X, Y, Z in the general formula (2). , W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ can be exemplified by the same substituents. Examples of the phosphino group include dimethylphosphino, diphenylphosphino, methylphenoxyphosphino and the like.

The phosphinyl group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms. Examples of the substituent include X, Y, Z in the general formula (2). , W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ can be exemplified by the same substituents. Examples of the phosphinyl group include phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl and the like.

The phosphinyloxy group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms. Examples of the substituent include the above general formula (2) And the same substituents as mentioned for X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ . Examples of the phosphinyloxy group include diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.

The phosphinylamino group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms. Examples of the substituent include the above general formula (2) And the same substituents as mentioned for X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ . Examples of the phosphinylamino group include dimethoxyphosphinylamino and dimethylaminophosphinylamino.

The silyl group represented by R ₁ , R ₂ and W is preferably a substituted or unsubstituted silyl group having 3 to 30 carbon atoms. Examples of the substituent include X, Y and Z in the general formula (2). , W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ can be exemplified by the same substituents. Examples of the silyl group include trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl and the like.

Examples of the azo group represented by R ₁ , R ₂ and W include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo, and the like. .

Examples of the imide group represented by R ₁ , R ₂ and W include N-succinimide and N-phthalimide.

The phosphoryl group represented by R ₁ , R ₂ and W includes a phosphoryl group having a substituent and an unsubstituted phosphoryl group. Examples of the phosphoryl group include a phenoxyphosphoryl group and a phenylphosphoryl group.

  The total carbon number of the trivalent linking group is preferably 0 to 50, more preferably 0 to 30, and most preferably 0 to 10.

  In general formula (4), the preferable example of s is 1 or 2, and 1 is especially preferable. A preferred example of t is 0 or 1, with 0 being particularly preferred.

  In the general formula (4), preferred examples of the 5- to 6-membered heterocycle that G constitutes are preferably 5-membered or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic groups, Further, it may be condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms.

  Examples of the heterocyclic group represented by G include pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan. , Benzofuran, thiophene, benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazo Examples include lysine, thiazoline and sulfolane.

  More preferably, a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, and a triazine ring are preferable, and among them, a pyridine ring, a pyrimidine ring, and a triazine ring are preferable, and an s-triazine ring is most preferable.

When the heterocyclic group constituting G is a group that can further have a substituent, examples of the substituent include X, Y, Z, W ₀ , and W ₁ in the general formula (2). , W ₂ , W ₃ , and W ₄ can be exemplified by the same substituents. The same thing as the substituent which was mentioned when the heterocyclic group represented by the said General formula (2) is a group which can have a substituent further is mentioned.

  Regarding the preferred combination of substituents of the azo pigment represented by the general formula (4) of the present invention, a pigment in which at least one of various substituents is the above-mentioned preferred group is preferable, and more various substituents are described above. A pigment that is a preferred group is more preferred, and a pigment in which all substituents are the preferred groups is most preferred.

  A particularly preferable combination as the azo pigment represented by the general formula (4) of the present invention includes the following (A) to (L).

(A) G is preferably a 5- to 6-membered nitrogen-containing heterocycle, and particularly preferably an S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring. -A triazine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferred, and an S-triazine ring is most preferred.

(B) s represents an integer of 1 to 4, preferably an integer of 1 to 2, and most preferably 1.

(C) t represents an integer of 0 to 3, preferably 0 to 1, and most preferably 0.

(D) R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted total carbon atom. A C4 to C12 heterocyclic group is preferable, and among them, a linear alkyl group or a branched alkyl group having a total carbon number of C1 to C8 is preferable, particularly a methyl group, a secondary or tertiary alkyl group is preferable, a methyl group, A t-butyl group is most preferred.

(E) Het-1 and Het-2 are preferably groups independently selected from the aromatic heterocyclic groups (1) to (15) represented by the general formula (2), and among them, (1) , (2), (3), (4), (5), (6), (7), (8), (9), (10), (11) are preferred, especially (2), (5 ), (6), (7), (8), (9), (10) are preferable, and (2), (5), (6), (7), (10) are more preferable. 7) is most preferred.

(F) Particularly preferred as X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, and among them, a cyano group Or an alkylsulfonyl group having 1 to 12 carbon atoms, and a most preferred one is a cyano group.

(G) Y is a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total carbon number of C4 to C12. Of these, a heterocyclic group is preferable, and among them, a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms in total or a branched alkyl group is preferable, particularly a hydrogen atom or a C1 to C8 alkyl group is preferable, and a hydrogen atom is most preferable. preferable.

(H) Z is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, A substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferred, and a particularly preferred substituent is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.

(L) Particularly preferred as W ₀ is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, and among them, cyano Group, a methanesulfonyl group or a phenylsulfonyl group is preferable, and a cyano group is most preferable.

(Nu) W _{1 to} W ₄ are a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total group. A C4-C12 heterocyclic group is preferable, and among them, a hydrogen atom, a linear alkyl group having a total carbon number of C1-C8 or a branched alkyl group is preferable, and a hydrogen atom or a C1-C8 alkyl group is particularly preferable. A hydrogen atom is most preferred.

Of the azo pigments represented by the general formula (4), a pigment represented by the following general formula (6) is preferable.
Hereinafter, Formula (6) will be described in detail.
General formula (6)

In General Formula (6), R ₁ and R ₂ each independently represent a hydrogen atom or a monovalent substituent. Het-1 and Het-2 are each independently synonymous with Het-1 and Het-2 represented by the general formula (4). * Represents a binding site with the azo group in the general formula (6).

Hereinafter, R ₁ , R ₂ , Het-1 and Het-2 will be described in more detail.
Examples of substituents for R ₁ and R ₂ are independently the same as the examples of R ₁ and R _{2 in} the general formula (4), and preferred examples are also the same.
The heterocyclic groups represented by Het-1 and Het-2 are independently the same as the examples of Het-1 and Het-2 in the general formula (4), and preferred examples are also the same.
As for the preferred combination of substituents of the pigment represented by the general formula (6) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  A particularly preferable combination as the azo pigment represented by the general formula (6) of the present invention includes the following (A) to (G).

(A) R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total carbon. A C4 to C12 heterocyclic group is preferable, and among them, a linear alkyl group or a branched alkyl group having a total carbon number of C1 to C8 is preferable, particularly a methyl group, a secondary or tertiary alkyl group is preferable, a methyl group, A t-butyl group is most preferred.

(B) Het-1 and Het-2 are preferably groups independently selected from the aromatic heterocyclic groups (1) to (15) represented by the general formula (2), and among them, (1) , (2), (3), (4), (5), (6), (7), (8), (9), (10), (11) are preferred, especially (2), (5 ), (6), (7), (8), (9), (10) are preferable, and (2), (5), (6), (7), (10) are more preferable. 7) is most preferred.

(C) Particularly preferred as X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, and among them, a cyano group Or an alkylsulfonyl group having 1 to 12 carbon atoms, and a most preferred one is a cyano group.

(D) Y is a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total carbon number of C4 to C12. Of these, a heterocyclic group is preferable, and among them, a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms in total or a branched alkyl group is preferable, a hydrogen atom or a C1 to C8 alkyl group is particularly preferable, and a hydrogen atom is most preferable.

(E) Z is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, A substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferred, and a particularly preferred substituent is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.

(F) Particularly preferable as W ₀ is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms. Group, a methanesulfonyl group or a phenylsulfonyl group is preferable, and a cyano group is most preferable.

(G) W _{1 to} W ₄ are a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total group. A C4-C12 heterocyclic group is preferable, and among them, a hydrogen atom, a linear alkyl group having a total carbon number of C1-C8 or a branched alkyl group is preferable, and a hydrogen atom or a C1-C8 alkyl group is particularly preferable. A hydrogen atom is most preferred.

The azo pigments represented by the general formulas (4) and (6) can take several tautomers in terms of chemical structure, but the ultimate structural formulas represented by the general formulas (4) and (6) Taking it off is preferable from the viewpoint of solvent resistance when used as a pigment. Although a mixture containing tautomers other than the structures represented by the general formulas (4) and (6) may be used, the tautomer content is preferably 30% or less, more preferably 10 % Or less, and most preferably 0%.
Specific examples of the azo pigments represented by the general formulas (4) and (6) (illustrated azo pigments Pig-1 to Pig-23) are shown below, but the azo pigments of the present invention are limited to the following examples. It is not something.

  The structures of the following specific examples are shown in the form of the ultimate structural formula among several tautomers that can be taken from the chemical structure, but used as a mixture containing tautomers other than the described structures. Needless to say.

Below, the manufacturing method of this invention is demonstrated in detail.
The production method of the azo pigment of the present invention is carried out by a coupling reaction between a diazonium compound obtained by diazonium-izing a heterocyclic amine represented by the following general formula (1) and a compound represented by the following general formula (3). In the method for producing an azo pigment represented by the formula (4), a coupling reaction is performed in the presence of sulfuric acid.
General formula (1)
Het-NH ₂
(In the formula, Het is synonymous with a heterocyclic group selected from the group of aromatic heterocycles represented by the following general formula (2). * Represents a binding site with an amino group in the general formula (1). To express.)
General formula (2):

(In General Formula (2), X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ each independently represent a hydrogen atom or a substituent.)
General formula (3)

(In the formula, R ₁ and R ₂ each independently represent a hydrogen atom or a monovalent substituent. G represents an atomic group capable of constituting a 5- to 6-membered heterocycle. W represents a heterogeneous group composed of G. Represents a substituent that can be bonded to the ring, s represents an integer of 1 to 4, t represents an integer of 0 to 3, and s + t is an integer of 4 or less.)
General formula (4)

(In General Formula (4), R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. G represents an atomic group capable of constituting a 5- to 6-membered heterocycle. W represents G. Represents a substituent that can be bonded to a heterocyclic ring, s represents an integer of 1 to 4, t represents an integer of 0 to 3, and s + t is an integer of 4 or less, Het-1 and Het-2 are independent of each other. Represents a group selected from the group of aromatic heterocyclic groups represented by the general formula (2), and * represents a bonding site with an azo group in the general formula (4).

In the general formula (1), Het is synonymous with Het-1 and Het-2 represented by the general formula (4), and preferred examples are also the same. * Represents a binding site with an amino group in the general formula (1).
In the general formula (2), X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , W ₄ are X, Y, Z, W ₀ , W ₁ , represented by the general formula (2), W _{2, W} 3, _{W 4} in the above formula, preferred examples are also the same.
In General Formula (3), R ₁ and R ₂ have the same meanings as R ₁ and R ₂ represented by General Formula (4), and preferred examples are also the same.
The example of the substituent of G is synonymous with the example of G in the said General formula (4), and its preferable example is also the same.
W is synonymous with the example of W in the said General formula (4), and its preferable example is also the same.
s and t are synonymous with the example of s and t in the said General formula (4), and a preferable example is also the same.

  As for the preferred combination of substituents of the intermediate of the azo pigment represented by the general formula (1) or general formula (3) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferable. More preferred are compounds in which more various substituents are the preferred groups, and most preferred are compounds in which all substituents are the preferred groups.

  Particularly preferred combinations as intermediates of the azo pigments represented by the general formula (1) and general formula (3) of the present invention include the following (A) to (N).

(A) G is preferably a 5- to 6-membered nitrogen-containing heterocycle, and particularly preferably an S-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or pyrrole ring. -A triazine ring, a pyrimidine ring, a pyridazine ring or a pyrazine ring is preferred, and an S-triazine ring is most preferred.

(B) s represents an integer of 1 to 4, preferably 1 or 2, and most preferably 1.

(C) t represents an integer of 0 to 3, preferably 0 or 1, and most preferably 0.

(D) R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 12 carbon atoms, a substituted or unsubstituted aryl group having 6 to 18 carbon atoms, or a substituted or unsubstituted total carbon atom. A C4 to C12 heterocyclic group is preferable, and among them, a linear alkyl group or a branched alkyl group having a total carbon number of C1 to C8 is preferable, particularly a methyl group, a secondary or tertiary alkyl group is preferable, a methyl group, A t-butyl group is most preferred.

(E) Het-1 and Het-2 are preferably groups independently selected from the aromatic heterocyclic groups (1) to (15) represented by the general formula (2), and among them, (1) , (2), (3), (4), (5), (6), (7), (8), (9), (10), (11) are preferred, especially (2), (5 ), (6), (7), (8), (9), (10) are preferable, and (2), (5), (6), (7), (10) are more preferable. 7) is most preferred.

(F) Particularly preferred as X is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, and among them, a cyano group Or an alkylsulfonyl group having 1 to 12 carbon atoms, and a most preferred one is a cyano group.

(G) Y is a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total carbon number of C4 to C12. Of these, a heterocyclic group is preferable, and among them, a hydrogen atom, a linear alkyl group having 1 to 8 carbon atoms in total or a branched alkyl group is preferable, particularly a hydrogen atom or a C1 to C8 alkyl group is preferable, and a hydrogen atom is most preferable. preferable.

(H) Z is a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, a substituted or unsubstituted aralkyl group, A substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group is preferred, and a particularly preferred substituent is a substituted or unsubstituted aryl group or a substituted or unsubstituted heterocyclic group.

(L) Particularly preferred as W ₀ is a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms, and among them, cyano Group, a methanesulfonyl group or a phenylsulfonyl group is preferable, and a cyano group is most preferable.

(Nu) W _{1 to} W ₄ are a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted total group. A C4-C12 heterocyclic group is preferable, and among them, a hydrogen atom, a linear alkyl group having a total carbon number of C1-C8 or a branched alkyl group is preferable, and a hydrogen atom or a C1-C8 alkyl group is particularly preferable. A hydrogen atom is most preferred.

Diazoniumation can be carried out by conventional methods.
For example, diazoniumation of a compound represented by the following general formula (7) is performed in a reaction medium containing an acid (for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc.). A conventional diazonium compound forming method using a nitrosonium ion source such as nitrous acid, nitrite or nitrosylsulfuric acid can be applied.
General formula (7):

More preferable examples of the acid include a case where acetic acid, propionic acid, methanesulfonic acid, phosphoric acid and sulfuric acid are used alone or in combination, and among them, phosphoric acid or a combined system of acetic acid and phosphoric acid is particularly preferable. .
Preferable examples of the reaction medium (solvent) include organic acids and inorganic acids, and phosphoric acid, acetic acid, propionic acid, and methanesulfonic acid are particularly preferable. Among them, acetic acid and / or propionic acid are preferable.
As an example of a preferable nitrosonium ion source, a diazonium compound (diazonium salt) can be stably and efficiently prepared by using nitrosylsulfuric acid in the preferable acid-containing reaction medium.

0.5-50 mass times is preferable, as for the usage-amount of the solvent with respect to the diazonium salt of General formula (7), More preferably, it is 1-20 mass times, and 3-15 mass times is especially preferable.
In the present invention, the heterocyclic amine of the general formula (1) may be in a state where it is dispersed in a solvent, or may be in a solution state depending on the kind of the heterocyclic amine.
The amount of the nitrosonium ion source used is preferably 0.95 to 5.0 equivalents, more preferably 1.00 to 3.00 equivalents, and particularly 1.00 to 1.50 equivalents relative to the heterocyclic amine. It is preferable.
The reaction temperature is preferably -15 ° C to 30 ° C, more preferably -10 ° C to 10 ° C, and further preferably -5 ° C to 5 ° C. Less than −10 ° C. is not economical because the reaction rate is remarkably slow and the time required for the synthesis is remarkably increased, and it is preferable to synthesize at a high temperature exceeding 30 ° C. because the amount of by-products increases. Absent.
The reaction time is preferably 30 minutes to 300 minutes, more preferably 30 minutes to 200 minutes, and still more preferably 30 minutes to 150 minutes.

  The coupling reaction (azo pigmentation step) can be carried out in an acidic reaction medium to a basic reaction medium, but the azo pigment of the present invention is preferably carried out in an acidic to neutral reaction medium, particularly When carried out in an acidic reaction medium, decomposition of the diazonium salt can be suppressed and the azo pigment can be efficiently derived.

In the method for producing an azo pigment of the present invention, coupling is performed in the presence of sulfuric acid.
By using sulfuric acid, the tautomers and crystal polymorphs of the obtained azo pigment can be controlled with good reproducibility. The amount of sulfuric acid to be used is preferably 0.1% by mass or more, more preferably 1.0% by mass or more, and particularly preferably 2 to 25% by mass with respect to the usage amount of the reaction solvent.
Sulfuric acid may be added at the time of diazoniumation, or may be added as a part or all of the reaction medium immediately before the coupling reaction. Further, sulfuric acid may be generated as a reaction by-product during diazonium formation. An example of a compound that generates sulfuric acid as a reaction by-product during diazoniumation is nitrosylsulfuric acid.

As a preferable example of the reaction medium (solvent), an organic acid, an inorganic acid, or an organic solvent can be used, but an organic solvent is particularly preferable, and a solvent that does not cause a liquid separation phenomenon during the reaction and presents a uniform solution with the solvent. preferable. For example, alcoholic organic solvents such as methanol, ethanol, propanol, isopropanol, butanol, t-butyl alcohol, amyl alcohol, ketone organic solvents such as acetone, methyl ethyl ketone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene Diol-based organic solvents such as glycol and 1,3-propanediol, ether-based organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol diethyl ether, tetrahydrofuran, dioxane, acetonitrile, and the like. May be a mixture of two or more.
Preferably, the organic solvent has a polarity parameter (ET) value of 40 or more. Among them, a glycol solvent having two or more hydroxyl groups in the solvent molecule, or an alcohol solvent having 3 or less carbon atoms, preferably an alcohol solvent having 2 or less carbon atoms (for example, methanol, ethylene glycol) is used. preferable. These mixed solvents are also included.
The amount of the solvent used is preferably 1 to 200 times by mass of the coupling component represented by the general formula (3). In the present invention, the coupling component of the general formula (3) needs to be in the state of a solution.

The amount of the coupling component used is preferably 0.95 to 5.00 equivalents, more preferably 1.00 to 3.00 equivalents, particularly 1.00 to 1.50 equivalents of the diazonium compound per azo coupling site. It is preferable that
The reaction temperature is preferably −30 ° C. to 40 ° C., more preferably −10 ° C. to 30 ° C., and further preferably −5 ° C. to 25 ° C. Less than −30 ° C. is not economical because the reaction rate is remarkably slow and the time required for synthesis is remarkably long, and it is preferable to synthesize at a high temperature exceeding 40 ° C. because the amount of by-products increases. Absent.
The reaction time is preferably 30 minutes to 8 hours, more preferably 1 hour to 6 hours, and still more preferably 1 hour to 4 hours.

In the production method of the present invention, the heterocyclic amine represented by the general formula (1) is preferably a compound represented by the following general formula (5).
General formula (5):

(In general formula (5), Y represents a hydrogen atom or a substituent.)
In General Formula (5), Y and a substituent are synonymous with Y and a substituent represented by the said General formula (5), and their preferable examples are also the same.

In the production method of the present invention, the pigment represented by the general formula (4) is preferably a pigment represented by the following general formula (6).
General formula (6):

(In General Formula (6), R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. Het-1 and Het-2 each independently represent an aromatic heterocycle represented by General Formula (2). Represents a group selected from the group of ring groups, * represents a bonding site with an azo group in the general formula (6).
In General Formula (6), R ₁ and R ₂ have the same meanings as R ₁ and R ₂ represented by General Formula (6), and preferred examples are also the same.

In the method for synthesizing azo pigments of the present invention, the product (crude azo pigment) obtained by these reactions may be subjected to a normal organic synthesis reaction post-treatment method and then purified or used without purification. it can.
That is, for example, the product liberated from the reaction system can be used without being purified, or can be purified by recrystallization, salt formation, etc., alone or in combination.

After completion of the reaction, the reaction solvent is distilled off, or it is poured into water or ice without being distilled off, and the liberated product is extracted with neutralization or without neutralization, or extracted with an organic solvent / aqueous solution. It can also be used after purification or refining by recrystallization, crystallization, salt formation or the like, either alone or in combination.
Since the azo pigment represented by the general formula (4) produced by the method of the present invention is obtained as a crude azo pigment, it is more preferable to carry out post-treatment. Examples of post-processing methods include, for example, solvent particle milling process such as solvent salt milling, salt milling, dry milling, solvent milling, acid pasting, solvent heat treatment, etc., resin, surfactant and dispersant. The surface treatment process by etc. is mentioned.

  The azo pigment represented by the general formula (4) produced by the method of the present invention is preferably subjected to a solvent heating treatment as a post-treatment. Examples of the solvent used in the solvent heat treatment include water, aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene and o-dichlorobenzene, and alcohols such as isopropanol and isobutanol. Examples thereof include solvents, polar aprotic organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone, glacial acetic acid, pyridine, and mixtures thereof. It is preferable to adjust the average particle diameter of the pigment to 0.01 μm to 1 μm by these post-treatments.

(Colorant composition)
The colorant composition of the present invention contains at least one azo pigment represented by the general formula (4) or (6), a salt or a hydrate thereof. Examples of the colorant composition of the present invention include colorants for polymers such as printing inks, paints, and plastics including masterbatches, color toners for electrophotography, inks for inkjets, resist inks for color filters, and colorants for cosmetics. Is mentioned. The colorant composition of the present invention contains a resin and / or a liquid medium as required in addition to the azo pigment represented by the general formula (4) or (6), a salt or a hydrate thereof. Also good. As the resin, any resin conventionally used in various applications such as the above-described various inks, paints, and color toners can be used, and is not particularly limited. The liquid medium may be water or an organic solvent, and any conventionally used medium can be used and is not particularly limited. In the colorant composition of the present invention, the azo pigment represented by the general formula (4) or (6), a salt or a hydrate thereof is preferably dispersed in the resin and / or liquid medium. A dispersing device is preferably used for dispersion. Examples of the dispersing device that can be used include a ball mill, a sand mill, a bead mill, a roll mill, a jet mill, a paint shaker, an attritor, an ultrasonic dispersing machine, a disper, a pressure heating kneader, A single screw extruder, a twin screw extruder, etc. are mentioned.

  Applications of the azo pigments of the present invention include image recording materials for forming images, particularly color images. Specifically, the ink-jet recording materials described in detail below, thermal recording materials, Pressure recording material, recording material using an electrophotographic method, transfer type silver halide photosensitive material, printing ink, recording pen, etc., preferably an ink jet recording material, a thermal recording material, a recording material using an electrophotographic method, More preferred are ink jet recording materials.

  The present invention can also be applied to a solid-state image pickup device such as a CCD, a color filter for recording / reproducing a color image used in a display such as an LCD or PDP, and a dyeing solution for dyeing various fibers.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples at all. In the examples, “parts” represents parts by weight.

[Example 1]
(Production of Pig-1)
3.7 parts of 5-amino-3-methyl-1,2,4-thiadiazole was added to 35 parts of phosphoric acid and heated to 50 ° C. to dissolve. This solution was ice-cooled and kept at -1 ° C, and 1.8 parts of concentrated sulfuric acid was added dropwise. After completion of the dropwise addition, 2.8 parts of sodium nitrite was added and stirred for 1 hour to obtain a diazonium salt solution. Separately, a suspension obtained by adding 4.0 parts of the compound represented by the formula (7) to 80 parts of methanol was prepared, and the above diazonium salt solution was added thereto at 2 to 10 ° C. over 10 minutes. The reaction was continued for 1 hour at 10 ° C., and the resulting powder was filtered off. This powder was added to 300 parts of water, and excess acid was neutralized with an aqueous potassium hydroxide solution. Filtration was performed again to obtain a yellow powder. This yellow powder was added to a mixed solvent of 40 parts of N, N-dimethylacetamide and 40 parts of water and aged by heating at 85 ° C. for 4 hours. This aging solution was filtered while hot, and further washed with methanol to obtain 3.7 parts (yield 55.2%) of an azo pigment represented by the formula (9). The result of purity analysis by HPLC was 95.8% (area ratio). When the same operation was repeated three times, a compound showing the same powder X-ray diffraction spectrum was obtained.

[Example 2]
4.0 parts 5-amino-3-methyl-1,2,4-thiadiazole was added to a mixture of 13.3 parts phosphoric acid and 26.6 parts acetic acid and heated to 50 ° C. to dissolve. This solution was ice-cooled and kept at −3 ° C., and 13.2 parts of a 40% sulfuric acid solution of nitrosylsulfuric acid was added and stirred for 1 hour to obtain a diazonium salt solution. At this time, 5-amino-3-methyl-1,2,4-thiadiazole and nitrosylsulfuric acid reacted to produce sulfuric acid as a by-product.
Separately, a suspension obtained by adding 5.0 parts of the compound represented by the formula (8) to 150 parts of methanol was prepared, and the above diazonium salt solution was added thereto at 2 to 10 ° C. over 10 minutes. The reaction was continued for 1 hour at 10 ° C., and the resulting powder was filtered off. This powder was added to 300 parts of water, and excess acid was neutralized with an aqueous potassium hydroxide solution. Filtration was performed again to obtain a yellow powder. This yellow powder was added to a mixed solvent of 50 parts of N, N-dimethylacetamide and 50 parts of water and aged by heating at 85 ° C. for 4 hours. This aging solution was filtered while hot, and further washed with methanol to obtain 5.9 parts (yield: 70.2%) of an azo pigment represented by the formula (9). The result of purity analysis by HPLC was 97.5% (area ratio). When the same operation was repeated three times, a compound showing the same powder X-ray diffraction spectrum was obtained.

[Comparative Example 1]
In Example 1, the azo pigment (9) was produced in the same manner except that 3.0 g of sodium nitrite was added instead of the 40% nitrosylsulfuric acid solution. When sodium nitrite was added, foaming occurred and brown smoke was generated. The yield of the obtained azo pigment (9) was 70.5%. The result of purity analysis by HPLC was 93.8% (area ratio). When the same operation was repeated three times, a solid having a powder X-ray diffraction spectrum different from the other two was obtained, and reproducibility could not be obtained.
From the above results, the production method of the present invention can obtain an azo pigment with high reproducibility and quality and high chemical purity.

[Example 3]
In the same manner as in Example 2, except that 5-amino-3-phenyl-1,2,4-thiadiazole was used instead of 5-amino-3-methyl-1,2,4-thiadiazole, Pig- 4 was obtained with a yield of 64.2%.

[Example 4]
In Example 1, except that 5-amino-4-cyano-1-phenylpyrazole was used instead of 5-amino-3-methyl-1,2,4-thiadiazole, The pigment obtained was obtained in 48.9% yield.

[Example 5]
In the same manner as in Example 1, except that 5-amino-4-cyano-3-methyl-1-phenylpyrazole was used instead of 5-amino-3-methyl-1,2,4-thiadiazole, Pig The pigment represented by −10 was obtained in a yield of 51.2%.

[Example 6]
In Example 2, the same except that 5-amino-4-cyano-3-methyl-1- (2-pyridyl) pyrazole was used instead of 5-amino-3-methyl-1,2,4-thiadiazole Thus, a pigment represented by Pig-12 was obtained in a yield of 71.8%.

[Example 7]
In Example 1, it is represented similarly as Pig-17 except that 2-amino-4-cyano-3-methylthiazole was used instead of 5-amino-3-methyl-1,2,4-thiadiazole. The pigment obtained was obtained in a yield of 32.9%.

[Example 8]
In Example 2, except that 5-amino-3-methyl-1,2,4-triazole was used instead of 5-amino-3-methyl-1,2,4-thiadiazole, Pig- The pigment represented by 19 was obtained with a yield of 47.6%.

3 is a powder X-ray diffraction spectrum of Pig-1 obtained by the method of Example 2. FIG. 4 is a powder X-ray diffraction spectrum diagram of Pig-4 obtained by the method of Example 3. FIG. 6 is a powder X-ray diffraction spectrum of Pig-9 obtained by the method of Example 4. FIG. 6 is a powder X-ray diffraction spectrum view of Pig-10 obtained by the method of Example 5. FIG. 6 is a powder X-ray diffraction spectrum view of Pig-12 obtained by the method of Example 6. FIG. 6 is a powder X-ray diffraction spectrum view of Pig-17 obtained by the method of Example 7. FIG. 6 is a powder X-ray diffraction spectrum view of Pig-19 obtained by the method of Example 8. FIG. 2 is a graph of a powder X-ray diffraction spectrum of Pig-1 obtained by the method of Comparative Example 1. FIG.

Claims (6)

An azo pigment represented by the following general formula (4) by a coupling reaction between a diazonium compound obtained by diazonium-izing a heterocyclic amine represented by the following general formula (1) and a compound represented by the following general formula (3) A process for producing an azo pigment represented by the following general formula (4), wherein a coupling reaction is carried out in the presence of sulfuric acid.
General formula (1):
Het-NH ₂
(In general formula (1), Het represents a group selected from the group of aromatic heterocyclic groups represented by the following general formula (2). * Represents a binding site with an amino group in general formula (1). .)
General formula (2):

(In General Formula (2), X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ each independently represent a hydrogen atom or a substituent.)
General formula (3):

(In General Formula (3), R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. G represents an atomic group capable of constituting a 5- to 6-membered heterocycle. W represents G. And represents a substituent that can be bonded to the heterocycle, s represents an integer of 1 to 4, t represents an integer of 0 to 3, and s + t is an integer of 4 or less.)
General formula (4):

(In General Formula (4), R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. G represents an atomic group capable of constituting a 5- to 6-membered heterocycle. W represents G. Represents a substituent that can be bonded to a heterocyclic ring, s represents an integer of 1 to 4, t represents an integer of 0 to 3, and s + t is an integer of 4 or less, Het-1 and Het-2 are independent of each other. Represents a group selected from the group of aromatic heterocyclic groups represented by the general formula (2), and * represents a bonding site with an azo group in the general formula (4).   The production method according to claim 1, wherein the heterocyclic amine represented by the general formula (1) is diazoniumized using nitrosylsulfuric acid. The method according to claim 1 or 2, wherein the heterocyclic amine represented by the general formula (1) is a compound represented by the following general formula (5).
General formula (5):

(In general formula (5), Y represents a hydrogen atom or a substituent.) The production method according to claim 1, wherein the azo pigment represented by the general formula (4) is an azo pigment represented by the following general formula (6).
General formula (6):

(In General Formula (6), R ₁ and R ₂ each independently represents a hydrogen atom or a substituent. Het-1 and Het-2 each independently represent an aromatic heterocycle represented by General Formula (2). Represents a group selected from the group of ring groups, * represents a bonding site with an azo group in the general formula (6).   An azo pigment represented by the general formula (4), a salt or a hydrate thereof, which is produced by the production method according to claim 1.   A colorant composition comprising at least one azo pigment, salt or hydrate thereof according to claim 5.

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