JP2009242489A - Azo pigment, pigment dispersion including the same, coloring composition and ink-jet recording ink - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a coloring composition and an ink-jet recording ink, excellent in chromatic characteristics such as coloring power and hue. <P>SOLUTION: The azo pigment represented by general formula (1), a salt thereof, a hydrate and a tautomer thereof are provided. In general formula (1), R<SB>1</SB>, P<SB>1</SB>and Q<SB>1</SB>each independently represent a hydrogen atom or a substituent; G represents an atomic group which can compose an aromatic hydrocarbon ring in which a 5- or 6-membered heterocycle is condensed; W represents a substituent which can be bound to the aromatic hydrocarbon ring, in which the heterocycle composed by G is condensed; and t represents an integer of 0-5. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to an azo pigment, a pigment dispersion coloring composition containing the azo pigment, and an ink for inkjet recording.

  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 dyes are used as pigments, they are further substantially insoluble in water and organic solvents and have good chemical fastness, and preferable absorption characteristics in a molecular dispersion state even when used as particles. It is also necessary to have properties such as not impairing.
The required characteristics can be controlled by the strength of intermolecular interaction, but it is difficult to achieve both because they are in a trade-off relationship.

  In addition, when a dye is used as a pigment, it has a particle size and a particle shape necessary for expressing desired transparency or concealment, fastness under environmental conditions used, for example, Light resistance, heat resistance, resistance to oxidizing gases such as ozone, chemical fastness to other organic solvents and sulfurous acid gas, etc., and dispersion to fine particles in the medium used Properties such as a stable state are also required. Since these properties are greatly influenced not only by the chemical structure but also by the particle size, particle shape, and crystallinity, these controls are very important (see, for example, Patent Document 1). 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.

  In other words, 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. As a result, the group of compounds that can be used as pigments is extremely limited compared to dyes, and even if high-performance dyes are derived into pigments, there are only a few that can satisfy the required performance as fine particle dispersions. It cannot be developed. This is confirmed by the fact that the number of pigments registered in the color index is less than 1/10 of the number of dyes.

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

  Patent Document 5 discloses a dye having an absorption characteristic 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.

  When full color is expressed using the subtractive color mixing method with three colors of yellow, magenta and cyan, or four colors with black added, if a pigment with poor fastness is used as the yellow pigment, the printed matter will be printed over time. If a pigment having a poor color characteristic is used, the color reproducibility during printing is deteriorated. Therefore, in order to obtain a printed matter that maintains a high color reproducibility for a long period of time, a yellow pigment and a pigment dispersion having both color characteristics and fastness are desired.

JP 2004-26930 A 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 relates to an azo pigment excellent in color characteristics such as coloring power and hue, and excellent in durability such as light resistance and ozone resistance, a pigment dispersion containing the azo pigment, a coloring composition, and an ink jet recording ink. The purpose is to provide.

  As a result of intensive studies in view of the above circumstances, the present inventors have obtained a novel azo pigment, which has been found to be excellent in both color characteristics and durability, and further, an azo pigment having a specific dye structure Has been found to satisfy the required performance as a pigment at a high level when used as a pigment, and the present invention has been completed.

[1]
An azo pigment represented by the following general formula (1), a salt thereof, a hydrate, and a tautomer thereof.
General formula (1):

(In General Formula (1), R ₁ , P ₁ and Q ₁ each independently represents a hydrogen atom or a substituent. G constitutes an aromatic hydrocarbon ring in which a 5- to 6-membered heterocycle is condensed. W represents a substituent that can be bonded onto the aromatic hydrocarbon ring to which the heterocyclic ring that constitutes G is condensed, t represents an integer of 0 to 5. Het. 1 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 (1), and n is 1 to 1. It represents an integer of 3. When n = 2, it represents a dimer via R ₁ , P ₁ , Q ₁ , W, G or Het.1, and when n = 3, R ₁ , P ₁ , Represents a trimer via Q ₁ , W, G or Het.
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.)
[2]
The azo pigment represented by the general formula (1) is an azo pigment represented by the following general formula (3), the azo pigment according to [1], a salt, a hydrate thereof, and the like Tautomers of.
General formula (3):

(In General Formula (3), W ₁₁ , W ₁₂ , W ₁₃ , and R ₁ each independently represent a hydrogen atom or a substituent. G ′ is a 5- to 6-membered hetero ring that can be condensed to an aromatic hydrocarbon ring. Represents a non-metallic atomic group capable of constituting a ring, W represents a substituent which can be bonded to the heterocyclic ring formed by G ′, t represents an integer of 0 to 4. Het. 1] represents a group selected from the group of aromatic heterocyclic groups represented by the general formula (2) described in 1.] in the general formula (2) is a bond with an azo group in the general formula (3). N represents an integer of 1 to 3. When n = 2, it represents a dimer via R ₁ , W, W ₁₁ , W ₁₂ , W ₁₃ , G ′ or Het.1. (When n = 3, it represents a trimer via R ₁ , W, W ₁₁ , W ₁₂ , W ₁₃ , G ′ or Het.)
[3]
The azo pigment according to [1] or [2], wherein the azo pigment represented by the general formula (1) or the general formula (3) is an azo pigment represented by the following general formula (4): Pigments, their salts, hydrates and their tautomers.
General formula (4):

(In General Formula (4), W ₁₁ , W ₁₂ , W ₁₃ , R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom or a substituent. Het. 1 is a general formula described in [1]. Represents a group selected from the group of aromatic heterocyclic groups represented by (2), wherein * in the general formula (2) represents a bonding site with an azo group in the general formula (4); It represents an integer of ˜3, and when n = 2, it represents a dimer via R ₁ , R ₂ , R ₃ , W, W ₁₁ , W ₁₂ , W ₁₃ or Het. The case represents a trimer via R ₁ , R ₂ , R ₃ , W, W ₁₁ , W ₁₂ , W ₁₃ or Het. 1)
[4]
The azo pigment according to [1] or [2], wherein the azo pigment represented by the general formula (1) or the general formula (3) is an azo pigment represented by the following general formula (5): Pigments, their salts, hydrates and their tautomers.
General formula (5):

(In the general formula (5), W ₁₁ , W ₁₂ , W ₁₃ , R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom or a substituent. Het. 1 is the general formula described in [1]. Represents a group selected from the group of aromatic heterocyclic groups represented by (2), wherein * in the general formula (2) represents a bonding site with an azo group in the general formula (5), and n represents 1. Represents an integer of ˜3, in the case of n = 2, it represents a dimer through R ₁ , R ₂ , R ₃ , W ₁₁ , W ₁₂ , W ₁₃ or Het. (Represents a trimer via R ₁ , R ₂ , R ₃ , W, W ₁₁ , W ₁₂ , W ₁₃ or Het.)
[5]
In the azo pigments represented by the general formula (1), (3), (4) or the general formula (5), Het. The azo group according to any one of [1] to [4], wherein the aromatic heterocyclic group represented by 1 represents an aromatic heterocyclic group represented by the following general formula (6): Pigments, salts, hydrates and tautomers thereof.
General formula (6):

(In General Formula (6), Y represents a hydrogen atom or a substituent. X represents an electron-withdrawing group having a Hammett's σp value of 0.2 or more. G ′ represents a 5- to 6-membered nitrogen-containing hetero group. This represents a group of nonmetallic atoms that can form a ring, and the heterocycle may be unsubstituted or substituted, and each heterocycle may be monocyclic or condensed. (* Represents a bonding site with an azo group.)
[6]
A pigment dispersion comprising at least one of the azo pigments according to any one of [1] to [5], salts thereof, hydrates, and tautomers thereof.
[7]
A coloring composition comprising at least one of the azo pigments, salts, hydrates and tautomers thereof according to any one of [1] to [5].
[8]
An ink for inkjet recording, comprising at least one of the azo pigments, salts, hydrates, and tautomers thereof according to any one of [1] to [5].

  ADVANTAGE OF THE INVENTION According to this invention, the azo pigment which is excellent in color characteristics, such as coloring power and a hue, and is excellent also in durability, such as light resistance and ozone resistance, is provided. By dispersing the azo pigment of the present invention in various media, a pigment dispersion having excellent color characteristics, durability and dispersion stability is provided. Moreover, according to this invention, the coloring composition which is excellent in color characteristics, such as coloring power and a hue containing this azo pigment, and is excellent also in durability, such as light resistance and ozone resistance, is provided. In particular, the azo pigment dispersion is used for, for example, printing inks such as inkjet, color toners for electrophotography, displays such as LCDs and PDPs, color filters used in image pickup devices such as CCDs, paints, and colored plastics. be able to.

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 “Chemicals” 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 (8) 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 in the present invention is represented by the general formula (1).

Hereinafter, the azo pigment represented by the general formula (1), its salt, hydrate and tautomers thereof will be described in detail.
General formula (1):

(In General Formula (1), R ₁ , P ₁ and Q ₁ each independently represents a hydrogen atom or a substituent. G constitutes an aromatic hydrocarbon ring in which a 5- to 6-membered heterocycle is condensed. W represents a substituent that can be bonded onto the aromatic hydrocarbon ring to which the heterocyclic ring that constitutes G is condensed, t represents an integer of 0 to 5. Het. 1 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 (1), and n is 1 to 1. It represents an integer of 3. When n = 2, it represents a dimer via R ₁ , P ₁ , Q ₁ , W, G or Het.1, and when n = 3, R ₁ , P ₁ , Represents a trimer via Q ₁ , W, G or Het.
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 (1) will be described in more detail.

In general formula (1), R ₁ , P ₁ , and Q ₁ each independently represent a hydrogen atom or a substituent.

n represents an integer of 1 to 3. When n = 2, R ₁ , P ₁ , Q ₁ , W, G or Het. 1 represents a dimer via 1. When n = 3, R ₁ , P ₁ , Q ₁ , W, G or Het. 1 represents a trimer through 1. When n is 1, R ₁ , P ₁ , Q ₁ , W, W ₀ , X, Y, Z, and G preferably represent a monovalent group. When n is 2, R ₁ , P ₁ , Q ₁ , W, W ₀ , X, Y, Z, G represent a monovalent or divalent substituent, and at least one represents a divalent substituent. It is preferable to represent. When n is 3, R ₁ , P ₁ , Q ₁ , W, W ₀ , X, Y, Z, G represent a monovalent, divalent, or trivalent substituent, and at least two are divalent substituents It is preferred that it represents a group or at least one represents a trivalent substituent.

The integer of 1 to 3 represented by n is preferably an integer of n = 1 to 2, and most preferably n = 1.

  G represents an atomic group capable of constituting an aromatic hydrocarbon ring in which a 5- or 6-membered heterocycle is condensed.

  W represents a substituent that can be bonded to an aromatic hydrocarbon ring in which the heterocycle formed by G is condensed.

  Preferable G in the general formula (1) is not particularly limited as long as it can be condensed to an aromatic hydrocarbon ring as a 5- to 6-membered heterocycle. Among them, an aromatic hydrocarbon ring in which a heterocycle containing -NHCO-, -NHCONH-, -CONH2, -NHCO-CO-NH-, and -CO-NH-CO- is condensed is preferable, and especially -NHCO- , -NHCONH-, an aromatic hydrocarbon ring having a condensed heterocycle containing -NHCONH-CO-NH- is preferable, and among them, an aromatic hydrocarbon ring in which a 5- to 6-membered heterocycle is particularly preferable is condensed. Include those represented by the following general formula (7) and / or general formula (8). In the formula, * represents a bonding site with the N atom in the general formula (1).

(In General Formulas (7) and (8), W ₁₁ , W ₁₂ , W ₁₃ , R ₂ and R ₃ each independently represent a hydrogen atom or a substituent.)

Examples of the substituent when W ₁₁ , W ₁₂ , W ₁₃ , R ₂ and R ₃ represent a substituent in the general formulas (7) and (8) include X and Y in the following general formula (2) , Z, W ₀ , W ₁ , W ₂ , W ₃ , W ₄ and the same substituents as mentioned above can be mentioned.

  t represents the number of groups that can be bonded to the heterocyclic group (an integer of 0 to 5), preferably an integer of 0 to 4, particularly preferably 0 to 3, and most preferably 0 to 2.

  Het. 1 represents a group selected from the aromatic heterocyclic group groups (1) to (15) represented by the general formula (2). * Represents a binding site with the azo group in the general formula (1).

  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 preferred, and (2), (6) and (7) are most preferred 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 when the group represented by R ₁ , P ₁ , Q ₁ , X, Y, Z, W, W ₀ , W ₁ , W ₂ , W ₃ , W ₄ represents a substituent. , Each independently a linear or branched alkyl group having 1 to 12 carbon atoms, a linear or branched aralkyl group having 7 to 18 carbon atoms, a linear or branched alkenyl group having 2 to 12 carbon atoms, or 2 to 2 carbon atoms. 12 straight or branched alkynyl groups, 3 to 12 straight or branched cycloalkyl groups, 3 to 12 straight or branched cycloalkenyl groups (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 atom (eg, chlorine atom, bromine) Atom), aryl group ( For example, phenyl, 4-t-butylphenyl, 2,4-di-t-amylphenyl), a heterocyclic group (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 group (for example, phenoxy, 2-methyl) Phenoxy, 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, phenoxy) Nylsulfonylamino, p-toluenesulfonylamino), carbamoyl group (eg, N-ethylcarbamoyl, N, N-dibutylcarbamoyl), sulfamoyl group (eg, N-ethylsulfamoyl, N, N-dipropylsulfamoyl), N-phenylsulfamoyl), sulfonyl groups (for example, methylsulfonyl, octylsulfonyl, phenylsulfonyl, p-toluenesulfonyl), alkyloxycarbonyl groups (for example, methoxycarbonyl, butyloxycarbonyl), heterocyclic oxy groups (for example, 1-phenyltetrazole-5-oxy, 2-tetrahydropyranyloxy), azo group (for example, phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenyl) Zo), acyloxy group (for example, acetoxy), carbamoyloxy group (for example, N-methylcarbamoyloxy, N-phenylcarbamoyloxy), silyloxy group (for example, trimethylsilyloxy, dibutylmethylsilyloxy), aryloxycarbonylamino group ( For example, phenoxycarbonylamino), imide group (for example, N-succinimide, N-phthalimide), heterocyclic thio group (for example, 2-benzothiazolylthio, 2,4-di-phenoxy-1,3,5-triazole) -6-thio, 2-pyridylthio), sulfinyl group (for example, 3-phenoxypropylsulfinyl), phosphonyl group (for example, phenoxyphosphonyl, octyloxyphosphonyl, phenylphosphonyl), aryloxycarbonyl group (for example, Phenoxycarbonyl), an acyl group (e.g., acetyl, 3-phenylpropanoyl, benzoyl), ionic hydrophilic groups (e.g., carboxyl group, a sulfo group, a phosphono group and a quaternary ammonium group).

  When the azo pigment of the present invention contains an ionic hydrophilic group as a substituent, it is preferably a salt with a polyvalent metal cation (eg, magnesium, calcium, barium), particularly preferably a lake pigment. .

In general formula (2), examples of preferred 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 acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, 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 , Halogenated alkoxy groups, halogenated aryloxy groups, halogenated alkylamino groups, halogenated alkylthio groups, aryl groups substituted with other electron-withdrawing groups having a σp value of 0.20 or more, heterocyclic groups, halogens Atoms, azo groups, or selenocyanes 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. , Aryloxycarbonyl group having 7 to 18 carbon atoms, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, arylsulfinyl group having 6 to 18 carbon atoms, alkylsulfonyl having 1 to 12 carbon atoms Group, arylsulfonyl group having 6 to 18 carbon atoms, sulfamoyl group having 0 to 12 carbon atoms, halogenated alkyl group having 1 to 12 carbon atoms, halogenated alkyloxy group having 1 to 12 carbon atoms, and 1 to 12 carbon atoms A halogenated alkylthio group, a halogenated aryloxy group having 7 to 18 carbon atoms, a carbon number of 7 substituted with two or more other electron-withdrawing groups having a 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 (1), preferred examples of R ₁ , P ₁ , Q ₁ and W will be described in detail.

  When a plurality of W are present, they each independently represent a substituent.

R ₁ , P ₁ and Q ₁ each independently represents a hydrogen atom or a substituent.

When R ₁ , P ₁ , Q ₁ and W represent a monovalent substituent, examples of the monovalent substituent are independently a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, 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, arylsulfonylamino group Alkylthio 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 or phosphoryl group, each of which may further have a substituent.

Among these, particularly preferred W is independently a 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, especially hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, hydroxyl group, alkylsulfonyl group, arylsulfonyl group, heterocyclic group or alkoxy group A carbonyl group is preferable, and an alkyl group, an aryl group, a hydroxyl group, and an alkoxycarbonyl group are most preferable.
R ₁ , P ₁ and Q ₁ are each independently hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, alkoxy group, amide group, ureido group, alkylsulfonylamino group, aryl A sulfonylamino group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, or an alkoxycarbonyl group, particularly a hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, hydroxyl group, alkylsulfonyl group, arylsulfonyl Group, heterocyclic group or alkoxycarbonyl group is preferred, and a hydrogen atom, alkyl group, aryl group, hydroxyl group or alkoxycarbonyl group is most preferred.

Hereinafter, R ₁ , P ₁ , Q ₁ and W will be described in more detail.
The halogen atom represented by R ₁ , P ₁ , Q ₁ 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 , P ₁ , Q ₁ 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 , P ₁ , Q ₁ 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 , P ₁ , Q ₁ 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 , P ₁ , Q ₁ 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 , P ₁ , Q ₁ 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 , P ₁ , Q ₁ 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-hexadeca. Noylaminophenyl. 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 , P ₁ , Q ₁ and W is a monovalent group in which one hydrogen atom is removed from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound. And 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, a substitution position. Benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, etc. It is done.

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

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

The aryloxycarbonyloxy group represented by R ₁ , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. (2) in the _{X, Y, Z, W 0} , W 1, W 2, W 3, W can be the same as the substituents exemplified in _4. Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy and the like.

The amino group represented by R ₁ , P ₁ , Q ₁ 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, 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 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 , P ₁ , Q ₁ and W is a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted aryl group having 6 to 30 carbon atoms. A carbonylamino group is preferable, and examples of the substituent include the same substituents as X, Y, Z, W ₀ , W ₁ , W ₂ , W ₃ , and W ₄ in the general formula (2). be able to. 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 , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted aminocarbonylamino group having 1 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 aminocarbonylamino group include carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino and the like.

The alkoxycarbonylamino group represented by R ₁ , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted alkoxycarbonylamino 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 alkoxycarbonylamino group include methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino and the like.

The aryloxycarbonylamino group represented by R ₁ , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. (2) in the _{X, Y, Z, W 0} , W 1, W 2, W 3, W can be the same as the substituents exemplified in _4. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino and the like.

The sulfamoylamino group represented by R ₁ , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. (2) in the _{X, Y, Z, W 0} , W 1, W 2, W 3, W can be the same as the substituents exemplified in _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 , P ₁ , Q ₁ and W are substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, and substituted or unsubstituted aryl groups having 6 to 30 carbon atoms. A sulfonylamino group is 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). be able to. 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 , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted alkylthio 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 can be the same as the substituents exemplified in _4. Examples of the alkylthio group include methylthio, ethylthio, n-hexadecylthio and the like.

The arylthio group represented by R ₁ , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted arylthio group having 6 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 arylthio group include phenylthio, p-chlorophenylthio, m-methoxyphenylthio and the like.

The heterocyclic thio group represented by R ₁ , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted heterocyclic thio 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 heterocyclic thio group include 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio and the like.

The sulfamoyl group represented by R ₁ , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted sulfamoyl group having 0 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 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 , P ₁ , Q ₁ and W are preferably substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms, and substituted or unsubstituted arylsulfinyl groups having 6 to 30 carbon atoms. As examples of the substituent, 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 given. 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 , P ₁ , Q ₁ 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 substituent, 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 given. Examples of the alkyl and arylsulfonyl groups include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl and the like.

The acyl group represented by R ₁ , P ₁ , Q ₁ and W is a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms. A heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms is preferable, and examples of the substituent include X, Y, Z, and W in the general formula (2). _The same substituents as mentioned for ₀ , W ₁ , W ₂ , W ₃ , and W ₄ can be mentioned. 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 , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted aryloxycarbonyl 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 aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl, and the like.

The alkoxycarbonyl group represented by R ₁ , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted alkoxycarbonyl 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 alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and the like.

The carbamoyl group represented by R ₁ , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted carbamoyl 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 can be the same as the substituents exemplified in _4. 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 , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted phosphino 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 phosphino group include dimethylphosphino, diphenylphosphino, methylphenoxyphosphino and the like.

The phosphinyl group represented by R ₁ , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted phosphinyl 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 phosphinyl group include phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl and the like.

The phosphinyloxy group represented by R ₁ , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms. (2) in the _{X, Y, Z, W 0} , W 1, W 2, W 3, W can be the same as the substituents exemplified in _4. Examples of the phosphinyloxy group include diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.

The phosphinylamino group represented by R ₁ , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms. (2) in the _{X, Y, Z, W 0} , W 1, W 2, W 3, W can be the same as the substituents exemplified in _4. Examples of the phosphinylamino group include dimethoxyphosphinylamino and dimethylaminophosphinylamino.

The silyl group represented by R ₁ , P ₁ , Q ₁ and W is preferably a substituted or unsubstituted silyl group having 3 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 silyl group include trimethylsilyl, t-butyldimethylsilyl, phenyldimethylsilyl and the like.

Examples of the azo group represented by R ₁ , P ₁ , Q ₁ and W include phenylazo, 4-methoxyphenylazo, 4-pivaloylaminophenylazo, 2-hydroxy-4-propanoylphenylazo, and the like. I can do it.

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

The phosphoryl group represented by R ₁ , P ₁ , Q ₁ 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.

Examples of the ionic hydrophilic group represented by R ₁ , P ₁ , Q ₁ and W include a sulfo group, a carboxyl group, a phosphono group and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include ammonium ion, alkali metal ion (eg, calcium ion, barium ion) and organic cation (eg, tetramethyl group). Anidium ion).

When R ₁ , P ₁ , Q ₁ and W represent a divalent group, examples of the divalent group include an alkylene group (eg, methylene, ethylene, propylene, butylene, pentylene), an alkenylene group (eg, ethenylene, pro Penylene), alkynylene groups (eg, ethynylene, propynylene), arylene groups (eg, phenylene, naphthylene), divalent heterocyclic groups (eg, 6-chloro-1,3,5-triazine-2,4-diyl group, pyrimidine-2) , 4-diyl group, pyrimidine-4, 6-diyl group, quinoxaline-2, 3-diyl group, pyridazine-3, 6-diyl), -O-, -CO-, -NR'- (R 'is a hydrogen atom, alkyl group or an aryl _{group), - S -, - SO} 2 -, - SO- , or a combination thereof (e.g., -NHCH ₂ CH ₂ NH -, - it is NHCONH-, etc.) Is preferred.

  The alkylene group, alkenylene group, alkynylene group, arylene group, divalent heterocyclic group, R alkyl group or aryl group may have a substituent.

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 alkyl group and aryl group of R ′ have the same meanings as the substituent examples given when R ₁ , P ₁ , Q ₁ and W are an alkyl group or an aryl group.

More preferably, an alkylene group having 10 or less carbon atoms, an alkenylene group having 10 or less carbon atoms, an alkynylene group having 10 or less carbon atoms, an arylene group having 6 to 10 carbon atoms, a divalent heterocyclic group, -S-,- More preferably, it is SO—, —SO ₂ — or a combination thereof (for example, —SCH ₂ CH ₂ S—, —SCH ₂ CH ₂ CH ₂ S—, etc.).

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

When R ₁ , P ₁ , Q ₁ and W represent a trivalent group, the trivalent group includes a trivalent hydrocarbon group, a trivalent heterocyclic group,> N-, or a divalent group thereof. A combination of groups (eg,> NCH ₂ CH ₂ NH—,> NCONH—, etc.) is preferred.

  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.

  Regarding the preferred combination of substituents of the pigment represented by the general formula (1) 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 (1) of the present invention includes the following (A) to (V).

(I) G is preferably a 5- to 6-membered nitrogen-containing heterocycle that can be bonded to an aromatic hydrocarbon ring, and particularly preferred G is —NHCO—, —NHCONH—, —CONH ₂ , —NHCO—CO—NH—. An aromatic hydrocarbon ring in which a hetero ring containing -CO-NH-CO- is condensed is preferable, and a hetero ring containing -NHCO-, -NHCONH-, -NHCO-CO-NH- is particularly condensed. Aromatic hydrocarbon rings are preferred, and among them, particularly preferred aromatic hydrocarbon rings in which a 5- to 6-membered heterocycle is condensed are those represented by the following general formula (7) and / or general formula (8). Can be mentioned. In the formula, * represents a bonding site with the N atom in the general formula (1).

(In the general formulas (7) and (8),
W ₁₁ , W ₁₂ , W ₁₃ , R ₂ and R ₃ each independently represent a hydrogen atom or a substituent. )

(B) W is a hydroxyl group, a cyano group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio Group, a substituted or unsubstituted arylthio group, and a carbonyl group (—CO—) are preferable, and in particular, a hydroxyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, and a carbonyl group. Of these, a hydroxyl group and a substituted amino group are most preferred.

(C) Preferred examples of W ₁₁ , W ₁₂ , W ₁₃ , R ₁ and R ₂ are each independently a hydrogen atom, hydroxyl group, cyano group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted amino group, substituted or An unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, and a carbonyl group (—CO—) are preferred, and particularly a hydrogen atom, a hydroxyl group, a substituted or unsubstituted group. A substituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group and a carbonyl group are preferred, and among them, a hydrogen atom, a hydroxyl group and a substituted amino group are most preferred.

(D) t represents the number of groups that can be bonded to the heterocyclic group (an integer of 0 to 5), preferably an integer of 0 to 4, particularly preferably 0 to 3, and most preferably 0 to 2 preferable.

(E) R ₁ is 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 heterocycle Among them, a straight chain alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, and a methyl group, a secondary or tertiary alkyl group is particularly preferable, and a methyl group or a t-butyl group is most preferable. preferable.

(F) P ₁ and Q ₁ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group In particular, a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted acyl group is preferable. Among them, a hydrogen atom is particularly preferable.

(G) Het.1 is preferably a group selected from the group of aromatic heterocyclic groups (1) to (15) represented by the general formula (2), among which (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, and (2), (6), (7) is most preferred.

(H) 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.

(Li) Y represents 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. Heterocyclic groups are preferable, and among them, a hydrogen atom, a linear alkyl group having a total carbon number of C1 to C8 or a branched alkyl group is preferable, and a hydrogen atom or a C1 to C8 alkyl group is particularly preferable. The group is most preferred.

(Nu) 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 heterocyclic group, and among them, a substituted or unsubstituted nitrogen-containing heterocyclic group is particularly preferred. Is preferred.

(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. Group, a methanesulfonyl group or a phenylsulfonyl group is preferable, and a cyano group is most preferable.

(W) W _{1 to} W ₄ are a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C18 aryl group, 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 pigment represented by the general formula (1) is preferably an azo pigment represented by the following general formula (3).
Hereinafter, the general formula (3) will be described in detail.
General formula (3)

In General Formula (3), W ₁₁ , W ₁₂ , W ₁₃ and R ₁ each independently represent a hydrogen atom or a substituent. G ′ represents a non-metallic atomic group capable of constituting a 5- to 6-membered heterocycle that can be condensed to an aromatic hydrocarbon ring. W represents a substituent that can be bonded onto the heterocycle formed by G ′. t represents an integer of 0 to 4. Het. 1 represents a group selected from the group of aromatic heterocyclic groups represented by the general formula (2) described above. * In the said General formula (2) represents the coupling | bond part with the azo group in General formula (3). n represents an integer of 1 to 3. When n = 2, R ₁ , R ₂ , R ₃ , W, W ₁₁ , W ₁₂ , W ₁₃ or Het. 1 represents a dimer via 1. When n = 3, R ₁ , R ₂ , R ₃ , W, W ₁₁ , W ₁₂ , W ₁₃ or Het. 1 represents a trimer through 1.

Hereinafter, R ₁ , G, W, t, and Het. 1 will be described in more detail.

Examples of the substituents of R ₁ are the same as examples of R ₁ in the general formula (1), and preferred examples are also the same.

  The example of the substituent of W is synonymous with the example of W in the said General formula (1), and its preferable example is also the same.

  The example of t is synonymous with the example of t in the said General formula (1), and its preferable example is also the same.

The nonmetallic atomic group represented by G ′ is not particularly limited as long as it is a 5- to 6-membered heterocycle that can be condensed to an aromatic hydrocarbon ring. Among them, heterocycles containing —NHCO—, —NHCONH—, —CONH ₂ , —NHCO—CO—NH—, —CO—NH—CO— are preferred, and in particular, —NHCO—, —NHCONH—, —NHCO—. Heterocycles containing CO—NH— are preferred, and among them, particularly preferred 5- to 6-membered heterocycles include those represented by the following general formula (9) and / or general formula (10). In the formula, * represents a condensation site with the aromatic hydrocarbon ring in the general formula (3).

(In general formulas (9) and (10), R ₂ and R ₃ each independently represents a hydrogen atom or a substituent.)

In the general formulas (9) and (10), examples of the substituent when R ₂ and R ₃ represent a 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.

  Het. The heterocyclic group represented by 1 is Het. It is synonymous with the example of 1, and a preferable example is also the same.

  Regarding the preferred combination of substituents of the pigment represented by the general formula (3) 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 preferred combination as the azo pigment and hydrazone pigment represented by the general formula (3) of the present invention includes the following (A) to (V).

(I) G ′ is not particularly limited as long as it is a 5- to 6-membered heterocycle that can be condensed to an aromatic hydrocarbon ring. Among them, heterocycles containing —NHCO—, —NHCONH—, —CONH ₂ , —NHCO—CO—NH—, —CO—NH—CO— are preferred, and in particular, —NHCO—, —NHCONH—, —NHCO—. Heterocycles containing CO—NH— are preferred, and among them, particularly preferred 5- to 6-membered heterocycles include those represented by the following general formula (9) and / or general formula (10). In the formula, * represents a condensation site with the aromatic hydrocarbon ring in the general formula (3).

(In general formulas (9) and (10), R ₂ and R ₃ each independently represents a hydrogen atom or a substituent.)

(B) W is a hydroxyl group, a cyano group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio Group, a substituted or unsubstituted arylthio group, and a carbonyl group (—CO—) are preferable, and in particular, a hydroxyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, and a carbonyl group. Of these, a hydroxyl group and a substituted amino group are most preferred.

(C) Preferred examples of W ₁₁ , W ₁₂ , W ₁₃ , R ₁ and R ₂ are each independently a hydrogen atom, hydroxyl group, cyano group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted amino group, substituted or An unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, and a carbonyl group (—CO—) are preferred, and particularly a hydrogen atom, a hydroxyl group, a substituted or unsubstituted group. A substituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group and a carbonyl group are preferred, and among them, a hydrogen atom, a hydroxyl group and a substituted amino group are most preferred.

(D) t represents the number of groups that can be bonded to a heterocyclic group (an integer of 0 to 4), preferably an integer of 0 to 3, particularly preferably 0 to 2, and most preferably 0 to 1 preferable.

(E) R ₁ is 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 heterocycle Among them, a straight chain alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, and a methyl group, a secondary or tertiary alkyl group is particularly preferable, and a methyl group or a t-butyl group is most preferable. preferable.

(F) Het. 1 is preferably a group selected from the group of aromatic heterocyclic groups (1) to (15) represented by the general formula (2), among which (1), (2), (3), (4) , (5), (6), (7), (8), (9), (10), (11) are preferred, and in particular, (2), (5), (6), (7), (8 ), (9) and (10) are preferred, and (2), (5), (6), (7) and (10) are more preferred, of which (2), (6) and (7) are the most. preferable.

(G) 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.

(H) 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.

(Li) 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 heterocyclic group, and among them, a substituted or unsubstituted nitrogen-containing heterocyclic group is particularly preferred. Is preferred.

(Nu) 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. Group, a methanesulfonyl group or a phenylsulfonyl group is preferable, and a cyano group is most preferable.

(L) 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.

(V) The pigment nucleus is preferably an azo pigment as the main component of the azo pigment and / or hydrazone pigment, and the single crystal form of the azo pigment nucleus is most preferable among the azo pigment nuclei.

The azo pigments represented by the general formulas (1) and (3) are preferably azo pigments represented by the following general formula (4) or (5).

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

(In the general formula (4), W ₁₁ , W ₁₂ , W ₁₃ , R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a substituent. Het. 1 represents the general formula according to claim 1. Represents a group selected from the group of aromatic heterocyclic groups represented by (2), wherein * in the general formula (2) represents a bonding site with an azo group in the general formula (4); It represents an integer of ˜3, and when n = 2, it represents a dimer via R ₁ , R ₂ , R ₃ , W, W ₁₁ , W ₁₂ , W ₁₃ or Het. The case represents a trimer via R ₁ , R ₂ , R ₃ , W, W ₁₁ , W ₁₂ , W ₁₃ or Het. 1)

Hereinafter, R ₁ , R ₂ , R ₃ , W ₁₁ , W ₁₂ , W ₁₃ and Het. 1 will be described in more detail.

Examples of the substituents of R ₁ are the same as examples of R ₁ in the general formula (3), and preferred examples are also the same.

Examples of substituents for W ₁₁ and W ₁₂ are the same as the examples of W in the general formula (3), and preferred examples are also the same.

  Het. The heterocyclic group represented by 1 is synonymous with the example of Het.1 in the general formula (3), and the preferred examples are also the same.

  Regarding the preferred combination of substituents of the pigment represented by the general formula (5) 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 (5) of the present invention includes the following (A) to (I).

(A) Preferred examples of W ₁₁ , W ₁₂ , W ₁₃ , R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, a cyano group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted amino group, substituted or An unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, and a carbonyl group (—CO—) are preferred, and particularly a hydrogen atom, a hydroxyl group, a substituted or unsubstituted group. A substituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group and a carbonyl group are preferred, and among them, a hydrogen atom, a hydroxyl group and a substituted amino group are most preferred.

(B) R ₁ is 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 heterocycle Among them, a straight chain alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, and a methyl group, a secondary or tertiary alkyl group is particularly preferable, and a methyl group or a t-butyl group is most preferable. preferable.

(C) Het. 1 is preferably a group selected from the group of aromatic heterocyclic groups (1) to (15) represented by the general formula (2), among which (1), (2), (3), (4) , (5), (6), (7), (8), (9), (10), (11) are preferred, and in particular, (2), (5), (6), (7), (8 ), (9) and (10) are preferred, and (2), (5), (6), (7) and (10) are more preferred, of which (2), (6) and (7) are the most. preferable.

(D) 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.

(E) Y represents 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.

(F) 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 heterocyclic group, and among them, a substituted or unsubstituted nitrogen-containing heterocyclic group is particularly preferred. Is preferred.

(G) 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.

(H) 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.

(I) As the pigment mother nucleus, the main component of the azo pigment and / or hydrazone pigment is preferably an azo pigment, and the single crystal type of the azo pigment mother nucleus is most preferable among the azo pigment mother nuclei.

Hereinafter, the azo pigment represented by the general formula (5), a tautomer thereof, a salt or a hydrate thereof will be described in detail.
General formula (5):

(In the general formula (5), W ₁₁ , W ₁₂ , W ₁₃ , R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom or a substituent. Het. 1 is the general formula according to claim 1. Represents a group selected from the group of aromatic heterocyclic groups represented by (2), wherein * in the general formula (2) represents a bonding site with an azo group in the general formula (5), and n represents 1. Represents an integer of ˜3.) When n = 2, R ₁ , R ₂ , R ₃ , W ₁₁ , W ₁₂ , W ₁₃ or Het. 1 represents a dimer via 1. When n = 3, R ₁ , R ₂ , R ₃ , W, W ₁₁ , W ₁₂ , W ₁₃ or Het. 1 represents a trimer through 1.

Hereinafter, R ₁ , R ₂ , R ₃ , W ₁₁ , W ₁₂ , W ₁₃ and Het. 1 will be described in more detail.

Examples of the substituents of R ₁ are the same as examples of R ₁ in the general formula (3), and preferred examples are also the same.

Examples of substituents for W ₁₁ and W ₁₂ are the same as the examples of W in the general formula (3), and preferred examples are also the same.

  Het. The heterocyclic group represented by 1 is synonymous with the example of Het.1 in the general formula (3), and the preferred examples are also the same.

  Regarding the preferred combination of substituents of the pigment represented by the general formula (5) 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 (5) of the present invention includes the following (A) to (I).

(A) Preferred examples of W ₁₁ , W ₁₂ , W ₁₃ , R ₁ and R ₂ are each independently a hydrogen atom, a hydroxyl group, a cyano group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted amino group, substituted or An unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, and a carbonyl group (—CO—) are preferred, and particularly a hydrogen atom, a hydroxyl group, a substituted or unsubstituted group. A substituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group and a carbonyl group are preferred, and among them, a hydrogen atom, a hydroxyl group and a substituted amino group are most preferred.

(B) R ₁ is 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 heterocycle Among them, a straight chain alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, and a methyl group, a secondary or tertiary alkyl group is particularly preferable, and a methyl group or a t-butyl group is most preferable. preferable.

(C) Het. 1 is preferably a group selected from the group of aromatic heterocyclic groups (1) to (15) represented by the general formula (2), among which (1), (2), (3), (4) , (5), (6), (7), (8), (9), (10), (11) are preferred, and in particular, (2), (5), (6), (7), (8 ), (9) and (10) are preferred, and (2), (5), (6), (7) and (10) are more preferred, of which (2), (6) and (7) are the most. preferable.

(D) 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.

(E) Y represents 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.

(F) 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 heterocyclic group, and among them, a substituted or unsubstituted nitrogen-containing heterocyclic group is particularly preferred. Is preferred.

(G) 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.

(H) 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.

(I) As the pigment mother nucleus, the main component of the azo pigment and / or hydrazone pigment is preferably an azo pigment, and the single crystal type of the azo pigment mother nucleus is most preferable among the azo pigment mother nuclei.

Of the azo pigments represented by the above general formulas (1) to (5), tautomers, salts or hydrates thereof, most preferably Het. The aromatic heterocyclic group represented by 1 is a pigment represented by the following general formula (6).

  Hereinafter, Formula (6) will be described in detail.

General formula (6):

(In General Formula (6), Y represents a hydrogen atom or a substituent. X represents an electron-withdrawing group having a Hammett's σp value of 0.2 or more. G ′ represents a 5- to 6-membered nitrogen-containing hetero group. This represents a group of nonmetallic atoms that can form a ring, and the heterocycle may be unsubstituted or substituted, and each heterocycle may be monocyclic or condensed. (* Represents a bonding site with an azo group.)

  Hereinafter, the X, Y, and G will be described in more detail.

  The example of the substituent of X is synonymous with the example of X in the said General formula (2), and its preferable example is also the same.

  The example of the substituent of Y is synonymous with the example of Y in the said General formula (2), and its preferable example is also the same.

Preferable examples of the nonmetallic atom group that can constitute the 5- to 6-membered nitrogen-containing heterocycle represented by G ′ are (G-1) to (G-13) in the following general formula (11). * In the general formulas (G-1) to (G-13) represents a bonding site with the N atom of the pyrazole ring. Z < ₁₁ > -Z < ₁₄ > represents a hydrogen atom or a substituent. G ′ in (G-13) represents a nonmetallic atom group that can form a 5- to 6-membered heterocycle, and the heterocycle represented by G ′ has a substituent even if it is unsubstituted. The heterocycle may be monocyclic or condensed. Formulas (G-1) to (G-13) may have tautomeric structures together with substituents.

General formula (11):

  * Represented by (G-1) to (G-13) in the general formula (11) represents a binding site with the N atom on the pyrazolyl group.

  In the above general formula (11), preferred examples of the nonmetallic atom group capable of constituting the 5- to 6-membered nitrogen-containing heterocycle represented by G ′ are (G-1), (G-2), (G -3), (G-4), (G-5), (G-6), (G-7), (G-10), (G-11), (G-12) are preferred, and ( G-1), (G-2), (G-3), (G-4), (G-5), and (G-6) are preferable, and (G-1), (G-3), (G-4) and (G-6) are preferable, and (G-1), (G-3) and (G-4) are the most preferable among them.

  Regarding the preferred combination of substituents of the aromatic heterocyclic group 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, A compound in which the substituent is the preferred group is more preferable, and a compound in which all the substituents are the preferred group is most preferable.

  A particularly preferable combination as the aromatic heterocyclic group represented by the general formula (6) of the present invention includes the following (A) to (C).

(I) 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.

(B) 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. Heterocyclic groups are preferable, and among them, a hydrogen atom, a linear alkyl group having a total carbon number of C1 to C8 or a branched alkyl group is preferable, and a hydrogen atom or a C1 to C8 alkyl group is particularly preferable. The group is most preferred.

(C) Preferred examples of the nonmetallic atom group that can constitute the 5- to 6-membered nitrogen-containing heterocycle represented by G ′ are (G-1), (G-2), (G-3), ( G-4), (G-5), (G-6), (G-7), (G-10), (G-11), (G-12) are preferred, and (G-1), (G-2), (G-3), (G-4), (G-5), and (G-6) are preferable, and (G-1), (G-3), and (G-4) are particularly preferable. (G-6) are preferred, and (G-1), (G-3) and (G-4) are most preferred.

The present invention includes in its scope tautomers of the azo pigments represented by the general formulas (1) to (6). The general formulas (1) to (6) are shown in the form of an ultimate structural formula among several tautomers that can be taken in terms of chemical structure, but are tautomers other than the described structures. Alternatively, it may be used as a mixture containing a plurality of tautomers.
For example, the pigment represented by the general formula (3) may be an azo-hydrazone tautomer represented by the following general formula (3 ′).
The present invention includes in its scope a compound represented by the following general formula (3 ′), which is a tautomer of the azo pigment represented by the general formula (3).

  Hereinafter, the general formulas (3) and (3 ′) will be described in detail.

(In general formula (3 ′), R ₁ , G ′, W, W ₁₁ , W ₁₂ , W ₁₃ , t, Het. 1 and n are the same as those defined in general formula (3).)

In the present invention, the azo pigments represented by the general formulas (1) to (6) may contain, for example, a tautomer represented by the above extreme structural formula. The main component is preferably one selected from pigments, salts thereof, hydrates and tautomers thereof. That is, it is preferable that the content of the azo pigment represented by a single ultimate structural formula is the main component, and the azo pigment represented by a different ultimate structure is small. 70% to 100%, preferably 80% to 100%, more preferably 90% to 100%, still more preferably 95% to 100, particularly preferably 100%. By using an azo pigment represented by a single limit structural formula as the main component, the regularity of the dye molecules is improved, and intramolecular and intermolecular interactions are strengthened to form higher-order three-dimensional networks. It is preferable in terms of performance required for the pigment, such as improvement in hue, light fastness, heat fastness, humidity fastness, oxidizing gas fastness and solvent resistance.
The mixing ratio of azo pigments, salts, hydrates and tautomers thereof is as follows: single crystal X-ray crystal structure analysis, powder X-ray diffraction (XRD), crystal micrograph (TEM), IR (KBr method) It can confirm from the physicochemical measurement value of solids, such as.

Many tautomers can be considered in the azo pigments represented by the general formulas (1) to (6). Among the azo pigments represented by the general formulas (1) to (6), as described above, examples of the particularly preferred general formula of the azo pigment include azo pigments represented by the following general formula (12) or (13). Can be mentioned.
The reason why this structure is preferable is that a nitrogen atom, a hydrogen atom, and a heteroatom (oxygen atom of a carbonyl group or an amino group) constituting a heterocycle contained in the azo pigment structure as represented by the general formula (12) or (13) (Nitrogen atom) can easily form at least one cross-over hydrogen bond (intramolecular hydrogen bond) in the molecule. As a result, the planarity of the molecule is improved, the intramolecular / intermolecular interaction is further improved, and the crystallinity of the azo pigment represented by the general formula (12) or (13) is increased (a higher order structure is formed). This is the most preferable example because the light fastness, thermal stability, wet heat stability, water resistance, gas resistance and / or solvent resistance, which are required performance as a pigment, are greatly improved.

Formula (12):

General formula (13):

(In the general formulas (12) and (13), X, Y, R ₁ and G ′ have the same meaning as defined in the general formula (3).)

  Specific examples of the azo pigments represented by the general formulas (1) to (6) are shown below, but the azo pigments used in the present invention are not limited to the following examples.

  The structures of the following specific examples are shown in the form of an ultimate structural formula among several tautomers that can be taken in terms of chemical structure, but have tautomeric structures other than those described. It goes without saying that it is also good.

  The pigments represented by the general formulas (1) to (6) of the present invention may have any chemical form as long as their chemical structural formulas are the general formulas (1) to (6) or tautomers thereof, and are also called polymorphs. It may be a pigment.

Crystal polymorphs refer to the same chemical composition but different arrangement of building blocks (molecules or ions) in the crystal. The crystal structure determines the chemical and physical properties, and each polymorph can be distinguished by its rheology, color, and other color characteristics. Different polymorphs can also be confirmed by X-Ray Diffraction (powder X-ray diffraction measurement results) and X-Ray Analysis (X-ray crystal structure analysis results).
When the crystalline polymorph exists in the pigment represented by the general formulas (1) to (6) of the present invention, it may be any polymorph, or may be a mixture of two or more polymorphs. The main component is preferably a single crystal type. That is, it is preferable that the polycrystal system is not mixed, and the content of the azo pigment having a single crystal type is 70% to 100%, preferably 80% to 100%, more preferably 90% with respect to the entire azo pigment. -100%, more preferably 95% -100, particularly preferably 100%. By using an azo pigment having a single crystal form as a main component, the regularity of the dye molecule arrangement is improved, the intramolecular / intermolecular interaction is strengthened, and a higher-order three-dimensional network is easily formed. . As a result, it is preferable in terms of performance required for pigments such as improvement of hue, light fastness, heat fastness, humidity fastness, oxidizing gas fastness and solvent resistance.
The mixing ratio of crystal polymorphs in azo pigments is based on solid physicochemical measurements such as single crystal X-ray crystal structure analysis, powder X-ray diffraction (XRD), crystal micrograph (TEM), IR (KBr method), etc. I can confirm.

  In the present invention, when the azo pigments represented by the general formulas (1) to (6) have an acid group, part or all of the acid group may be in a salt form. These pigments and free acid type pigments may be mixed. Examples of the salt type include salts of alkali metals such as Na, Li and K, ammonium salts optionally substituted with an alkyl group or hydroxyalkyl group, and organic amine salts. Examples of organic amines include lower alkyl amines, hydroxy-substituted lower alkyl amines, carboxy-substituted lower alkyl amines, and polyamines having 2 to 10 alkyleneimine units having 2 to 4 carbon atoms. In the case of these salt types, the type is not limited to one type, and a plurality of types may be mixed.

  Further, in the structure of the pigment used in the present invention, when a plurality of acid groups are contained in one molecule, the plurality of acid groups may be salt type or acid type and may be different from each other.

  In the present invention, the azo pigments represented by the general formulas (1) to (6) may be hydrates containing water molecules in the crystals.

The azo pigment represented by the general formula (1) can be produced by the following method. That is, the heterocyclic amine represented by the following general formula (14) is diazoniumized,
General formula (14):
Het-NH ₂
(In the formula, Het is synonymous with a heterocyclic group selected from the group of aromatic heterocycles represented by the general formula (2). * In the general formula (2) is the same as that in the general formula (14). This represents the binding site with the amino group.)
Then, the azo pigment represented by the said General formula (1) can be manufactured by performing a coupling reaction with the compound represented by the following general formula (15).
General formula (15):

(In the formula, R ₁ , P ₁ and Q ₁ each independently represents a hydrogen atom or a substituent. G represents an aromatic hydrocarbon ring condensed with a 5- to 6-membered heterocyclic ring. Represents a metal atom group, W represents a substituent that can be bonded to an aromatic hydrocarbon ring condensed with a hetero ring formed by G. t represents an integer of 0 to 5.)

In the general formula (15), R ₁ , P ₁ and Q ₁ have the same meanings as R ₁ , P ₁ and Q ₁ represented by the general formula (1), 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 (1), and its preferable example is also the same.
W is synonymous with the example of W in the said General formula (1), and its preferable example is also the same.
t is synonymous with the example of t in the said General formula (1), and its 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 (14) and general formula (15) 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 (14) and general formula (15) of the present invention include the following (a) to (v).

(I) G is preferably a 5- to 6-membered nitrogen-containing heterocycle that can be bonded to an aromatic hydrocarbon ring, and particularly preferred G is —NHCO—, —NHCONH—, —CONH ₂ , —NHCO—CO—NH—. An aromatic hydrocarbon ring in which a hetero ring containing -CO-NH-CO- is condensed is preferable, and a hetero ring containing -NHCO-, -NHCONH-, -NHCO-CO-NH- is particularly condensed. Aromatic hydrocarbon rings are preferred, and among them, particularly preferred aromatic hydrocarbon rings in which a 5- to 6-membered heterocycle is condensed are those represented by the following general formula (7) and / or general formula (8). Can be mentioned. In the formula, * represents a bonding site with the N atom in the general formula (1).

(In General Formulas (7) and (8), W ₁₁ , W ₁₂ , W ₁₃ , R ₂ and R ₃ each independently represent a hydrogen atom or a substituent.)

(B) W is a hydroxyl group, a cyano group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio Group, a substituted or unsubstituted arylthio group, and a carbonyl group (—CO—) are preferable, and in particular, a hydroxyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, and a carbonyl group. Of these, a hydroxyl group and a substituted amino group are most preferred.

(C) Preferred examples of W ₁₁ , W ₁₂ , W ₁₃ , R ₁ and R ₂ are each independently a hydrogen atom, hydroxyl group, cyano group, substituted or unsubstituted carbamoyl group, substituted or unsubstituted amino group, substituted or An unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio group, a substituted or unsubstituted arylthio group, and a carbonyl group (—CO—) are preferred, and particularly a hydrogen atom, a hydroxyl group, a substituted or unsubstituted group. A substituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group and a carbonyl group are preferred, and among them, a hydrogen atom, a hydroxyl group and a substituted amino group are most preferred.

(D) t represents the number of groups that can be bonded to a heterocyclic group (an integer of 0 to 5), preferably an integer of 1 to 4, particularly preferably 2 to 3, and most preferably 3 among them.

(E) R ₁ is 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 heterocycle Among them, a straight chain alkyl group having 1 to 8 carbon atoms or a branched alkyl group is preferable, and a methyl group, a secondary or tertiary alkyl group is particularly preferable, and a methyl group or a t-butyl group is most preferable. preferable.

(F) P ₁ and Q ₁ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or a substituted or unsubstituted arylsulfonyl group In particular, a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted acyl group is preferable. Among them, a hydrogen atom is particularly preferable.

(G) Het is preferably a group selected from the group of aromatic heterocyclic groups (1) to (15) represented by the general formula (2), among which (1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11) are preferable, and (2), (5), (6), (7) are particularly preferable. , (8), (9), and (10) are preferable, and (2), (5), (6), (7), and (10) are more preferable. Among them, (2), (6), (7 ) Is preferred, and (2) is most preferred.

(H) 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.

(Li) Y represents 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.

(Nu) 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 heterocyclic group, and among them, a substituted or unsubstituted nitrogen-containing heterocyclic group is particularly preferred. Is preferred.

(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. Group, a methanesulfonyl group or a phenylsulfonyl group is preferable, and a cyano group is most preferable.

(W) W _{1 to} W ₄ are a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C18 aryl group, 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.

Below, it demonstrates in detail regarding the synthesis | combination of the azo pigment of this invention.
The azo pigment of the present invention can be synthesized, for example, by reacting a diazonium salt prepared by a known method with a diazo component of the general formula (14) with a coupling component of the general formula (15).

The diazonium salt preparation and coupling reaction can be carried out by conventional methods.
The diazonium salt preparation of the general formula (14) is prepared, for example, in a reaction medium containing an acid (for example, hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc.) Conventional diazonium salt preparation methods using nitrous acid, nitrite or nitrosylsulfuric acid can be applied.

More preferred 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 sulfuric acid is particularly preferred.
Preferable examples of the reaction medium (solvent) include organic acids and inorganic acids, and phosphoric acid, sulfuric acid, acetic acid, propionic acid, and methanesulfonic acid are particularly preferable. Among these, acetic acid and / or propionic acid are preferable.
As an example of a preferable nitrosonium ion source, a diazonium salt can be stably and efficiently prepared by using nitrosylsulfuric acid in the above-mentioned preferable acid-containing reaction medium.

0.5-50 mass times is preferable, as for the usage-amount of the solvent with respect to the diazo component of General formula (14), More preferably, it is 1-20 mass times, and 3-10 mass times is especially preferable.
In the present invention, the diazo component of the general formula (14) may be in a state of being dispersed in a solvent, or may be in a solution state depending on the kind of the diazo component.
The amount of nitrosonium ion source used is preferably 0.95 to 5.0 equivalents, more preferably 1.00 to 3.00 equivalents, particularly 1.00 to 1.10 equivalents, relative to the diazo component. Is preferred.
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 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 in an acidic reaction medium. This suppresses the decomposition of the diazonium salt and can efficiently induce the azo pigment.

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 100 times by mass, more preferably 1 to 50 times by mass, and even more preferably 2 to 10 times by mass of the coupling component represented by the general formula (15).

In the present invention, the coupling component of the general formula (15) may be in a state of being dispersed in a solvent, or may be in a state of a solution depending on the type of the coupling component.
The amount of the coupling component used is preferably 0.95 to 5.0 equivalents, more preferably 1.00 to 3.00 equivalents, particularly 1.00 to 1.50, based on the azo coupling site. It is preferable that it is equivalent.

The reaction temperature is preferably -30 ° C to 30 ° C, more preferably -15 ° C to 10 ° C, and further preferably -10 ° C to 5 ° C. Less than −30 ° C. is not economical because the reaction rate is remarkably slow and the time required for synthesis becomes remarkably long. In addition, synthesis at a high temperature exceeding 30 ° C. is preferable 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.

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.

The method for synthesizing the azo pigment of the present invention will be described in more detail.
The method for producing an azo pigment of the present invention includes a coupling reaction of a diazonium compound obtained by diazonium-izing a heterocyclic amine represented by the following general formula (14) and a compound represented by the following general formula (15): The coupling reaction can be carried out after dissolving the compound of general formula (15) in an organic solvent.

  The diazonium reaction of the heterocyclic amine represented by the general formula (14) is performed, for example, in an acidic solvent such as sulfuric acid, phosphoric acid, acetic acid and the like with a reagent such as sodium nitrite and nitrosylsulfuric acid at a temperature of 15 ° C. or less for 10 minutes. It can be carried out by reacting for about 6 hours. The coupling reaction is performed by reacting the diazonium salt obtained by the above-described method with the compound represented by the general formula (15) at 40 ° C. or less, preferably 15 ° C. or less for about 10 minutes to 12 hours. Is preferred.

  The tautomerism and / or crystal polymorphism described above can be controlled by the production conditions during the coupling reaction. As a method for producing a crystal having a more preferable form, for example, it is preferable to use the method of the present invention in which the compound represented by the general formula (15) is once dissolved in an organic solvent and then a coupling reaction is performed. Examples of the organic solvent that can be used at this time include an alcohol solvent. As examples of the alcohol solvent, methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol and the like are preferable, and methanol is particularly preferable among them.

  Another method for producing an azo pigment of the present invention is a coupling reaction between a diazonium compound obtained by diazonium-izing a heterocyclic amine represented by the general formula (14) and a compound represented by the general formula (15). The coupling reaction can be carried out in the presence of a polar aprotic solvent.

  Examples of polar aprotic solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, and mixed solvents thereof. When these solvents are used, the compound of the general formula (15) may or may not be completely dissolved in the solvent.

  Although the compounds represented by the general formulas (1) to (6) are obtained as a crude azo pigment (crude) by the above production method, it is desirable to perform post-treatment when used as the pigment of the present invention. Examples of post-treatment methods include solvent salt milling, salt milling, dry milling, solvent milling, pigment particle control step by grinding treatment such as acid pasting, solvent heating treatment, resin, surfactant and dispersant. The surface treatment process by etc. is mentioned.

The compounds represented by the general formulas (1) to (6) of the present invention are preferably subjected to solvent heat treatment and / or solvent salt milling 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. An inorganic or organic acid or base may be further added to the solvents mentioned above. The temperature of the solvent heat treatment varies depending on the desired primary particle size of the pigment, but is preferably 40 to 150 ° C, more preferably 60 to 100 ° C. The treatment time is preferably 30 minutes to 24 hours.
As solvent salt milling, for example, a crude azo pigment, an inorganic salt, and an organic solvent that does not dissolve the crude azo pigment are charged into a kneader and kneaded and ground therein. As said inorganic salt, water-soluble inorganic salt can be used conveniently, For example, it is preferable to use inorganic salts, such as sodium chloride, potassium chloride, sodium sulfate. Moreover, it is more preferable to use an inorganic salt having an average particle size of 0.5 to 50 μm. The amount of the inorganic salt used is preferably 3 to 20 times by mass, more preferably 5 to 15 times by mass with respect to the crude azo pigment. As the organic solvent, a water-soluble organic solvent can be suitably used, and the solvent easily evaporates due to a temperature rise during kneading, so that a high boiling point solvent is preferable from the viewpoint of safety. Examples of such organic solvents include diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2- (methoxymethoxy) ethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, diethylene glycol Propylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene Glycol or mixtures thereof. The amount of the water-soluble organic solvent used is preferably 0.1 to 5 times by mass with respect to the crude azo pigment. The kneading temperature is preferably 20 to 130 ° C, particularly preferably 40 to 110 ° C. As the kneader, for example, a kneader or a mix muller can be used.

(Pigment dispersion)
The pigment dispersion of the present invention is characterized by containing at least one azo pigment represented by the general formulas (1) to (6). Thereby, it can be set as the pigment dispersion excellent in chromatic characteristics, durability, and dispersion stability.

  The pigment dispersion of the present invention may be aqueous or non-aqueous, but is preferably an aqueous pigment dispersion. As the aqueous liquid in which the pigment is dispersed in the aqueous pigment dispersion of the present invention, a mixture containing water as a main component and optionally adding a hydrophilic organic solvent can be used. Examples of the hydrophilic organic solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, sec-butanol, t-butanol, pentanol, hexanol, cyclohexanol, benzyl alcohol and other alcohols, ethylene glycol, diethylene glycol , Other alcohols such as triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butylene glycol, hexanediol, pentanediol, glycerin, hexanetriol, thiodiglycol, ethylene glycol monomethyl ether, ethylene glycol mono Ethyl ether, ethylene glycol butyl ether, diethylene glycol mono Chill ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl ether acetate triethylene glycol monoethyl ether, ethylene glycol monophenyl ether Glycol derivatives such as ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, morpholine, N-ethylmorpholine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyethyleneimine, tetramethylpropylenediamine Such as amine, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, 2-pyrrolidone, N-methyl-2-pyrrolidone, N-vinyl-2-pyrrolidone, 2-oxazolidone, 1 , 3-dimethyl-2-imidazolidinone, acetonitrile, acetone and the like.

  Further, the aqueous pigment dispersion of the present invention may contain an aqueous resin. Examples of the aqueous resin include a water-soluble resin that dissolves in water, a water-dispersible resin that disperses in water, a colloidal dispersion resin, or a mixture thereof. Specific examples of the aqueous resin include acrylic, styrene-acrylic, polyester, polyamide, polyurethane, and fluorine resins.

  In addition, surfactants and dispersants may be used to improve pigment dispersion and image quality. Examples of the surfactant include anionic, nonionic, cationic and amphoteric surfactants. Any surfactant may be used, but anionic or nonionic surfactants may be used. It is preferable to use it. Examples of anionic surfactants include fatty acid salts, alkyl sulfate esters, alkylbenzene sulfonates, alkyl naphthalene sulfonates, dialkyl sulfosuccinates, alkyl diaryl ether disulfonates, alkyl phosphates, and polyoxyethylene alkyls. Examples thereof include ether sulfate, polyoxyethylene alkylaryl ether sulfate, naphthalene sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate ester salt, glycerol borate fatty acid ester, polyoxyethylene glycerol fatty acid ester and the like.

  Nonionic surfactants include, for example, polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene oxypropylene block copolymer, sorbitan fatty acid ester, polyoxyethylene sorbitan fatty acid ester, polyoxyethylene sorbitol fatty acid ester, glycerin Examples include fatty acid esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, fluorine-based resins, and silicon-based materials.

  The non-aqueous pigment dispersion is obtained by dispersing the pigment represented by the general formula (1) in a non-aqueous vehicle. Resins used in non-aqueous vehicles are, for example, petroleum resins, casein, shellac, rosin modified maleic resin, rosin modified phenolic resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber, chlorinated rubber, oxidized rubber, hydrochloric acid rubber , Phenolic resin, alkyd resin, polyester resin, unsaturated polyester resin, amino resin, epoxy resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate copolymer, acrylic resin, methacrylic resin, polyurethane resin, silicone resin, fluorine resin , Drying oil, synthetic drying oil, styrene / maleic acid resin, styrene / acrylic resin, polyamide resin, polyimide resin, benzoguanamine resin, melamine resin, urea resin chlorinated polypropylene, butyral resin, vinylidene chloride resin and the like. A photocurable resin may be used as the non-aqueous vehicle.

  Examples of the solvent used in the non-aqueous vehicle include aromatic solvents such as toluene, xylene, and methoxybenzene, and acetates such as ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether acetate. Solvents, propionate solvents such as ethoxyethyl propionate, alcohol solvents such as methanol and ethanol, ether solvents such as butyl cellosolve, propylene glycol monomethyl ether, diethylene glycol ethyl ether, diethylene glycol dimethyl ether, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, etc. Ketone solvents, aliphatic hydrocarbon solvents such as hexane, N, N-dimethylformamide, γ-butyrolactam, N Methyl-2-pyrrolidone, aniline, nitrogen compound-based solvent such as pyridine, a lactone-based solvents such as γ- butyrolactone, carbamic acid esters such as a mixture of 48:52 of methyl carbamate and ethyl carbamate acid.

  In the present invention, the volume average particle diameter of the pigment is preferably 10 nm or more and 250 nm or less. The volume average particle diameter of the pigment particles refers to the particle diameter of the pigment itself or the particle diameter to which the additive has adhered when an additive such as a dispersant is attached to the colorant. In the present invention, a Nanotrac UPA particle size analyzer (UPA-EX150; manufactured by Nikkiso Co., Ltd.) was used as a measuring device for the volume average particle diameter of the pigment. The measurement was performed according to a predetermined measuring method by placing 3 ml of the pigment dispersion in a measuring cell. As parameters to be input for immediate presentation, ink viscosity was used for viscosity, and pigment density was used for the density of dispersed particles.

  A more preferable volume average particle diameter is 20 nm or more and 250 nm or less, and further preferably 30 nm or more and 230 nm or less. When the number average particle size of the particles in the pigment dispersion is less than 10 nm, there are cases where the storage stability cannot be ensured, whereas when it exceeds 250 nm, the optical density may be lowered.

  The concentration of the pigment contained in the pigment dispersion of the present invention is preferably in the range of 1 to 35% by mass, and more preferably in the range of 2 to 25% by mass. If the density is less than 1% by mass, sufficient image density may not be obtained when the pigment dispersion is used alone as the ink. If the concentration exceeds 35% by mass, the dispersion stability may decrease.

  The pigment dispersion of the present invention can be obtained by dispersing the above azo pigment and an aqueous or non-aqueous medium using a dispersing device. Dispersing devices include simple stirrer, impeller stirring method, in-line stirring method, mill method (for example, colloid mill, ball mill, sand mill, bead mill, attritor, roll mill, jet mill, paint shaker, agitator mill, etc.), ultrasonic method Further, a high-pressure emulsification dispersion system (high-pressure homogenizer; specific commercially available devices such as gorin homogenizer, microfluidizer, DeBEE2000, etc.) can be used.

  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.

  The monoazo pigments of the present invention are used by adjusting physical properties such as solvent resistance, dispersibility, and heat mobility suitable for the application with substituents. Further, the monoazo pigment of the present invention can be used in an emulsified dispersion state, and further in a solid dispersion state, depending on the system used.

(Coloring composition)
The colored composition of the present invention means a colored composition containing at least one azo pigment of the present invention. The coloring composition of the present invention can contain a medium, but when a solvent is used as the medium, it is particularly suitable as an ink for inkjet recording. The coloring composition of the present invention can be produced by using a lipophilic medium or an aqueous medium as a medium and dispersing the azo pigment of the present invention in the medium. Preferably, an aqueous medium is used. The coloring composition of the present invention includes an ink composition excluding a medium. The coloring composition of the present invention may contain other additives as necessary within a range that does not impair the effects of the present invention. Other additives include, for example, anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, anti-fungal agents, pH adjusters, surface tension adjusters, Known additives (described in JP-A No. 2003-306623) such as a foaming agent, a viscosity modifier, a dispersant, a dispersion stabilizer, a rust inhibitor, and a chelating agent can be used. These various additives are directly added to the ink liquid in the case of water-soluble ink. In the case of oil-soluble ink, it is common to add to the dispersion after preparation of the azo pigment dispersion, but it may be added to the oil phase or water phase at the time of preparation.

〔ink〕
Next, the ink of the present invention will be described.
The ink of the present invention contains the pigment dispersion of the present invention described above, and is preferably prepared by mixing a water-soluble solvent, water and the like. However, if there is no particular problem, the pigment dispersion of the present invention may be used as it is.
The ink of the present invention contains the pigment dispersion of the present invention and can also be used as an ink for inkjet recording.

  Further, the coloring composition containing the pigment of the present invention can be preferably used as an ink for inkjet recording.

  The ink of the present invention uses the pigment dispersion described above. Preferably, it is prepared by mixing a water-soluble solvent, water and the like. However, if there is no particular problem, the pigment dispersion of the present invention may be used as it is.

[Ink for inkjet recording]
Next, the ink for inkjet recording of the present invention will be described.

  The pigment dispersion described above is used for the inkjet recording ink of the present invention (hereinafter sometimes referred to as “ink”). Preferably, it is prepared by mixing a water-soluble solvent, water and the like. However, if there is no particular problem, the pigment dispersion of the present invention may be used as it is.

  The content ratio of the pigment dispersion in the ink of the present invention is preferably in the range of 1 to 100% by mass in consideration of the hue, color density, saturation, transparency and the like of the image formed on the recording medium. The range of mass% is particularly preferable, and the range of 3 to 10 mass% is most preferable among them.

  The azo pigment of the present invention is preferably contained in an amount of 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass in 100 parts by mass of the ink of the present invention. It is more preferable to contain -10 mass parts. Further, in the ink of the present invention, other pigments may be used in combination with the azo pigment of the present invention. When two or more kinds of pigments are used in combination, the total content of the pigments is preferably within the above range.

  The ink of the present invention can be used not only for monochromatic image formation but also for full color image formation. In order to form a full color image, a magenta color ink, a cyan color ink, and a yellow color ink can be used, and a black color ink may be further used to adjust the color tone.

  Furthermore, in the ink of the present invention, other pigments can be used simultaneously in addition to the azo pigment of the present invention. Examples of yellow pigments that can be applied include C.I. I. P. Y. -74, C.I. I. P. Y. -128, C.I. I. P. Y. -155, C.I. I. P. Y. -213, and applicable magenta pigments include C.I. I. P. V. -19, C.I. I. P. R. -122, and examples of applicable cyan pigments include C.I. I. P. B. -15: 3, C.I. I. P. B. -15: 4 can be mentioned, and apart from these, any one can be used. Applicable black materials include disazo, trisazo, and tetraazo pigments, as well as carbon black dispersions.

As the water-soluble solvent used in the ink jet recording ink of the present invention, polyhydric alcohols, polyhydric alcohol derivatives, nitrogen-containing solvents, alcohols, sulfur-containing solvents and the like are used.
Specific examples of polyhydric alcohols include ethylene glycol, diethylene glycol, propylene glycol, butylene glycol, triethylene glycol, 1,5-pentanediol, 1,2,6-hexanetriol, and glycerin.

  Examples of the polyhydric alcohol derivatives include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diethylene glycol Examples thereof include ethylene oxide adducts of glycerin.

  Examples of the nitrogen-containing solvent include pyrrolidone, N-methyl-2-pyrrolidone, cyclohexyl pyrrolidone, and triethanolamine. Examples of alcohols include alcohols such as ethanol, isopropyl alcohol, butyl alcohol, and benzyl alcohol. Examples of the solvent include thiodiethanol, thiodiglycerol, sulfolane, dimethyl sulfoxide and the like. In addition, propylene carbonate, ethylene carbonate, or the like can be used.

  The water-soluble solvent used in the present invention may be used alone or in combination of two or more. The content of the water-soluble solvent is 1% by mass or more and 60% by mass or less, preferably 5% by mass or more and 40% by mass or less of the entire ink. When the amount of the water-soluble solvent in the ink is less than 1% by mass, a sufficient optical density may not be obtained. Conversely, when the amount is more than 60% by mass, the viscosity of the liquid increases. In some cases, the ejection characteristics of the ink liquid become unstable.

Preferred physical properties of the ink for ink jet recording of the present invention are as follows.
The surface tension of the ink is preferably 20 mN / m or more and 60 mN / m or less. More preferably, it is 20 mN or more and 45 mN / m or less, More preferably, it is 25 mN / m or more and 35 mN / m or less. If the surface tension is less than 20 mN / m, liquid may overflow on the nozzle surface of the recording head, and printing may not be performed normally. On the other hand, if it exceeds 60 mN / m, the permeability to the recording medium after printing may be slow, and the drying time may be slow.
The surface tension was measured under the environment of 23 ° C. and 55% RH using a Wilhelmy surface tension meter as described above.

The viscosity of the ink is preferably from 1.2 mPa · s to 8.0 mPa · s, more preferably from 1.5 mPa · s to less than 6.0 mPa · s, still more preferably from 1.8 mPa · s to 4. It is less than 5 mPa · s. When the viscosity is greater than 8.0 mPa · s, the dischargeability may be reduced. On the other hand, when it is smaller than 1.2 mPa · s, the long-term jetting property may deteriorate.
The viscosity (including those described later) was measured using a rotational viscometer Rheomat 115 (manufactured by Contraves) at 23 ° C. and a shear rate of 1400 s ⁻¹ .

  In addition to the components described above, water is added to the ink in the range of the above-described preferable surface tension and viscosity. The amount of water added is not particularly limited, but is preferably 10% by mass to 99% by mass, and more preferably 30% by mass to 80% by mass with respect to the entire ink.

  Furthermore, if necessary, for the purpose of controlling properties such as ejection improvement, cellulose derivatives such as polyethyleneimine, polyamines, polyvinylpyrrolidone, polyethylene glycol, ethylcellulose, carboxymethylcellulose, polysaccharides and derivatives thereof, other water-soluble polymers, acrylics Polymer emulsion, polyurethane emulsion, polymer emulsion such as hydrophilic latex, hydrophilic polymer gel, cyclodextrin, macrocyclic amines, dendrimers, crown ethers, urea and its derivatives, acetamide, silicone surfactant, fluorine-based A surfactant or the like can be used.

In order to adjust conductivity and pH, compounds of alkali metals such as potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, triethanolamine, diethanolamine, ethanolamine, 2-amino-2-methyl Nitrogen-containing compounds such as -1-propanol, alkaline earth metal compounds such as calcium hydroxide, acids such as sulfuric acid, hydrochloric acid and nitric acid, strong acid and weak alkali salts such as ammonium sulfate, and the like can be used.
In addition, a pH buffer, an antioxidant, a fungicide, a viscosity modifier, a conductive agent, an ultraviolet absorber, and the like can be added as necessary.

[Inkjet recording method, inkjet recording apparatus, and ink tank for inkjet recording]
The ink jet recording method of the present invention is a method of forming an image on the surface of the recording medium by using the ink for ink jet recording of the present invention and ejecting ink from the recording head to the surface of the recording medium in accordance with a recording signal.
The ink jet recording apparatus of the present invention further includes a recording head that uses the ink for ink jet recording of the present invention and ejects ink (if necessary, a treatment liquid) onto the surface of the recording medium, and ejects the ink from the recording head onto the surface of the recording medium. By doing so, the apparatus forms an image. The ink jet recording apparatus of the present invention can supply ink to the recording head and can be removed from the ink jet recording apparatus main body (hereinafter referred to as “ink tank”). May be provided). In this case, the ink tank of the present invention is stored in the ink tank for ink jet recording.

As the ink jet recording apparatus of the present invention, a normal ink jet recording apparatus equipped with a printing method capable of using the ink for ink jet recording of the present invention can be used. In addition, the drying of the ink is controlled as necessary. Equipped with a heater, etc., or an intermediate transfer mechanism, and a mechanism for ejecting (printing) ink and processing liquid onto the intermediate and then transferring it to a recording medium such as paper. Also good.
In addition, the ink tank for ink jet recording of the present invention is detachable from an ink jet recording apparatus equipped with a recording head, and has a configuration capable of supplying ink to the recording head while being attached to the ink jet recording apparatus. For example, a conventionally known ink tank can be used.

The ink jet recording method (apparatus) of the present invention preferably adopts a thermal ink jet recording method or a piezo ink jet recording method from the viewpoint of the effect of improving bleeding and intercolor bleeding.
In the case of the thermal ink jet recording method, the ink is heated at the time of ejection and has a low viscosity, but the viscosity rapidly increases because the temperature of the ink is lowered on the recording medium. For this reason, there is an effect of improving bleeding and intercolor bleeding. On the other hand, in the case of the piezo ink jet method, it is possible to discharge a high-viscosity liquid, and the high-viscosity liquid can suppress spreading in the paper surface direction on the recording medium. There is an improvement effect on intercolor bleeding.

  In the ink jet recording method (apparatus) of the present invention, the replenishment (supply) of ink to the recording head is preferably performed from an ink tank filled with ink liquid (including a treatment liquid tank if necessary). The ink tank is preferably of a cartridge type that can be attached to and detached from the apparatus main body, and ink can be easily replenished by exchanging the cartridge type ink tank.

[Color toner]
The content of the monoazo pigment of the present invention in 100 parts by weight of the color toner of the present invention is not particularly limited, but is preferably 0.1 parts by weight or more, more preferably 1 to 20 parts by weight, and more preferably 2 to 10 parts by weight. It is most preferable to contain a part. As the binder resin for a color toner into which the monoazo pigment of the present invention is introduced, all commonly used binders can be used. Examples thereof include styrene resin, acrylic resin, styrene / acrylic resin, and polyester resin.
Inorganic fine powders and organic fine particles may be externally added to the toner for the purpose of improving fluidity and controlling charging. Silica fine particles and titania fine particles whose surface is treated with an alkyl group-containing coupling agent or the like are preferably used. These have a number average primary particle diameter of preferably 10 to 500 nm, and more preferably 0.1 to 20% by mass in the toner.

  As the release agent, all conventionally used release agents can be used. Specific examples include olefins such as low molecular weight polypropylene, low molecular weight polyethylene, and ethylene-propylene copolymer, microcrystalline wax, carnauba wax, sazol wax, and paraffin wax. These addition amounts are preferably 1 to 5% by mass in the toner.

  The charge control agent may be added as necessary, but is preferably colorless from the viewpoint of color development. Examples thereof include those having a quaternary ammonium salt structure and those having a calixarene structure.

  As the carrier, either an uncoated carrier composed only of magnetic material particles such as iron and ferrite, or a resin-coated carrier whose magnetic material particle surface is coated with a resin or the like may be used. The average particle size of the carrier is preferably 30 to 150 μm in terms of volume average particle size.

  The image forming method to which the toner of the present invention is applied is not particularly limited. For example, a method of forming a color image after repeatedly forming a color image on a photoconductor to form an image, or a method of forming an image on a photoconductor. For example, the image may be transferred to an intermediate transfer member and the like, and a color image may be formed on the intermediate transfer member and then transferred to an image forming member such as paper to form a color image.

[Thermal recording (transfer) material]
The heat-sensitive recording material includes an ink sheet in which the monoazo pigment of the present invention is coated on a support together with a binder, and an image-receiving sheet that fixes a pigment that has migrated in response to thermal energy applied from a thermal head in accordance with an image recording signal. Composed. The ink sheet can be formed by preparing an ink liquid by dispersing the monoazo pigment of the present invention in the form of fine particles in a solvent together with a binder, coating the ink on a support, and drying it appropriately. The amount of ink applied on the support is not particularly limited, but is preferably 30 to 1000 mg / m ² . As the preferred binder resin, ink solvent, support, and image receiving sheet, those described in JP-A-7-137466 can be preferably used.

  In order to apply the heat-sensitive recording material to a heat-sensitive recording material capable of full-color image recording, a cyan ink sheet containing a heat-diffusible cyan dye capable of forming a cyan image, and heat diffusion capable of forming a magenta image. It is preferable to form a magenta ink sheet containing a reactive magenta dye and a yellow ink sheet containing a heat diffusible yellow dye capable of forming a yellow image by sequentially coating the support. In addition, an ink sheet containing a black image forming substance may be further formed as necessary.

〔Color filter〕
As a color filter forming method, a pattern is first formed with a photoresist and then dyed, or disclosed in JP-A-4-163552, JP-A-4-128703, and JP-A-4-175653. Thus, there is a method of forming a pattern with a photoresist to which a dye is added. Any of these methods may be used as a method for introducing the coloring matter of the present invention into a color filter. Preferred methods are described in JP-A-4-175533 and JP-A-6-35182. The positive resist composition comprising a thermosetting resin, a quinonediazide compound, a cross-linking agent, a dye and a solvent, and after coating on a substrate, exposing through a mask and developing the exposed portion. Then, a positive resist pattern is formed, the positive resist pattern is exposed on the entire surface, and then the exposed positive resist pattern is cured, and a color filter forming method can be mentioned. In addition, a black matrix is formed according to a conventional method, and an RGB primary color system or Y, M, C complementary color system color filter can be obtained. In the case of a color filter, the amount of the monoazo pigment of the present invention is not limited, but is preferably 0.1 to 50% by mass.

Regarding the thermosetting resin, quinonediazide compound, crosslinking agent, and solvent used in this case, and those used, those described in the above-mentioned patent documents can be preferably used.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail based on an Example, this invention is not limited to these Examples at all.

[Synthesis Example 1] Synthesis of Exemplified Azo Pigment (Pig-1) The azo pigment (Exemplary Azo Pigment: Pig-1) of the present invention can be derived, for example, from the following synthetic route.

(1) Synthesis of compound b: A suspension of 7.5 g of compound (a) and 50 mL of concentrated hydrochloric acid (manufactured by Wako Pure Chemical Industries, Ltd.) was kept at an internal temperature of −2 to 0 ° C. under ice cooling, and sodium nitrite ( An aqueous solution in which 3.6 g (manufactured by Wako Pure Chemical Industries) was dissolved was dropped and stirred at the same temperature for 1 hour to obtain a diazonium salt solution. Next, 28.2 g of tin chloride dihydrate (manufactured by Wako Pure Chemical Industries, Ltd.) was suspended in 50 mL of concentrated hydrochloric acid, and the prepared diazonium salt solution was added dropwise thereto at an internal temperature of 3 ° C. or lower. After reacting at the same temperature for 0.5 hour, the ice bath was removed, the temperature was raised to room temperature, and the reaction was further continued for 2.0 hours. Thereafter, 50 mL of saturated saline was added at room temperature, followed by filtration, and washing with 50 mL of water cooled to an internal temperature of 5 ° C. to obtain white crystals. Methanol (50 mL) was added to the crystals, and the mixture was refluxed at an internal temperature of 60 ° C. for 1 hour and filtered at the same temperature. The obtained crystals were dried at room temperature for 8 hours to obtain 5.7 g of compound (b).
¹ H-NMR (DMSO-d6), δ value TMS standard: 6.62 to 6.68 (1H, m), 6.70 to 6.75 (1H, d), 6.82 to 6.88 (1H , D), 9.90 to 10.98 (3H, brs), 10.42 to 10.48 (1H, s), 10.50 to 10.57 (1H, s))

(2) Synthesis of compound Cp-1: To a suspension of 5.1 g of compound (b) and 75 mL of ethanol, 2.3 g of aminocrotonnitrile (manufactured by Wako Pure Chemical Industries, Ltd.) was added in portions at room temperature. The temperature was raised to 65 ° C. and refluxed at the same temperature for 5.0 hours. Thereafter, the mixture was allowed to cool to room temperature, the content was poured into 200 mL of water, and the precipitated crystals were separated by filtration and washed with 20 mL of methanol. Further, the obtained crystals were added to 20 mL of ethyl acetate, stirred at an internal temperature of 5 ° C. for 30 minutes, and filtered at the same temperature. The obtained crystal was dried at 60 ° C. for 3 hours to obtain 1.4 g of the compound (Cp-1).
¹ H-NMR (DMSO-d6), δ value TMS standard: 2.02 to 2.04 (3H, s), 5.05 to 5.12 (2H, brs), 5.20 to 5.23 (1H , S), 6.90 to 7.00 (1H, d), 7.03 to 7.12 (2H, m), 10.65 to 10.73 (2H, d))

(3) Synthesis of compound D-1:
5.9 g of ethoxymethylenemalononitrile (manufactured by ALDRICH) was dividedly added to 5 g of compound (B-1) (manufactured by Wako Pure Chemical Industries, Ltd.) and 25 mL of ethanol suspension at room temperature, and then the internal temperature was raised to 60 ° C. The mixture was refluxed for 3.0 hours, cooled to room temperature, filtered, washed with 100 mL of isopropyl alcohol, and the obtained crystals were dried at room temperature for 8 hours to obtain 7.1 g of compound (D-2). ¹ H-NMR (DMSO-d6), δ value TMS standard: 7.32 to 7.40 (1H, m), 7.80 to 7.90 (2H, m), 7.98 to 8.08 (1H , T), 8.07 to 8.18 (2H, brs), 8.45 to 8.53 (1H, t))

(4) Pig. Synthesis of -1:
0.6 g of (D-1) was added to 7 mL of phosphoric acid at room temperature, and then dissolved by heating to an internal temperature of 50 ° C. This solution was kept at an internal temperature of −2 to 0 ° C. under ice-cooling, 0.24 g of sodium nitrite was added in portions and stirred at the same temperature for 1 hour to obtain a diazonium salt solution. Next, 0.6 g of (Cp-1) was suspended in 20 mL of methanol, and the prepared diazonium salt solution was added dropwise thereto at an internal temperature of 3 ° C. or lower. After stirring at the same temperature for 2 hours, the resulting crystals were poured into 50 mL of water and separated by filtration. Subsequently, the obtained crystals were added to 10 mL of methanol and 10 mL of water without drying, refluxed at 60 ° C. for 1 hour, and filtered at the same temperature. Furthermore, it wash | cleaned with 10 mL of methanol, and the obtained crystal | crystallization was dried at 60 degreeC for 3 hours, and 0.7g of specific examples (Pig.-1) of this invention were obtained.

[Synthesis Example 2] Synthesis of Exemplified Azo Pigment (Pig-2) The azo pigment (Exemplary Azo Pigment: Pig-2) of the present invention can be derived, for example, from the following synthetic route.

(1) Synthesis of Compound Cp-2: Into a suspension of 3.0 g of Compound (b) obtained separately by the method of Synthesis Example 1 above and 60 ml of water, 2.1 g of pivaloylacetonitrile (Wako Pure Chemical Industries, Ltd.) was added at room temperature. Product) was added in portions, and then the temperature was raised to an internal temperature of 50 ° C., followed by stirring at the same temperature for 6.0 hours. Thereafter, the mixture was allowed to cool to room temperature, 1N aqueous potassium hydroxide solution was added to adjust the pH to 6, the contents were filtered, and washed with 30 ml of water and 20 ml of methanol. Further, the obtained crystal was dissolved in 100 mL of ethyl acetate and filtered. Crystals obtained by concentrating the filtrate were dried at 60 ° C. for 3 hours to obtain 2.9 g of compound (Cp-2).
¹ H-NMR (DMSO-d6), δ value TMS standard: 2.18 to 2.22 (9H, s), 5.05 to 5.10 (2H, s), 5.32 to 5.34 (1H , S), 6.90 to 6.98 (1H, d), 7.05 to 8.10 (2H, d), 10.62 to 10.72 (2H, brs))

(2) Pig. -2 synthesis:
1.0 g of (D-1) was added to 12 mL of phosphoric acid at room temperature, and then dissolved by heating to an internal temperature of 50 ° C. This solution was kept at an internal temperature of −2 to 0 ° C. under ice cooling, 0.4 g of sodium nitrite was added in portions and stirred at the same temperature for 1 hour to obtain a diazonium salt solution. Next, 1.3 g of (Cp-2) was suspended in 26 mL of methanol, and the prepared diazonium salt solution was added dropwise thereto at an internal temperature of 3 ° C. or lower. After stirring at the same temperature for 2.0 hours, the crystals formed by pouring into 80 mL of water were separated by filtration. Subsequently, the obtained crystals were added to 40 mL of methanol and 20 mL of water without drying, refluxed at 60 ° C. for 1 hour, and filtered at the same temperature. Furthermore, it wash | cleaned with 20 mL of methanol, and the obtained crystal | crystallization was dried at 60 degreeC for 3 hours, and 1.3 g of specific examples (Pig.-2) of this invention were obtained.

[Synthesis Example 3] Synthesis of Exemplified Azo Pigment (Pig-3) The azo pigment (Exemplary Azo Pigment: Pig-3) of the present invention can be derived, for example, from the following synthetic route.

(1) Synthesis of compound (B-2):
A solution of 26.2 g of hydrazine monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 30 mL of methanol was adjusted to an internal temperature of 10 ° C. Stir for hours. Thereafter, the internal temperature was raised to 40 ° C., followed by stirring for 1.0 hour. Subsequently, the mixture was allowed to cool to room temperature and 30 mL of water was added, followed by filtration and washing with 30 mL each of water and isopropyl alcohol. The obtained crystals were dried at room temperature for 8 hours to obtain 12.4 g of compound (B-2). ¹ H-NMR (DMSO-d6), δ value TMS standard 4.08 to 4.20 (2H, brs), 6.55 to 6.72 (2H, d), 8.10 to 8.15 (1H, s), 8.27-8.35 (2H, d))

(2) Synthesis of compound (D-2):
To 15.0 g of the compound (B-2) and 90 mL of ethanol suspension, 17.5 g of ethoxymethylenemalononitrile (manufactured by ALDRICH) was added in portions at room temperature, and then the internal temperature was raised to 60 ° C. Refluxed for 0.0 hours, then cooled to room temperature and filtered. Subsequently, it was washed with 40 mL of ethanol, and the obtained crystals were dried at 60 ° C. for 3 hours to obtain 21.9 g of compound (D-2). ¹ H-NMR (DMSO-d6), δ value TMS standard: 7.47 to 7.55 (1H, t), 7.95 to 7.98 (1H, s), 8.03 to 8.13 (2H , Brs), 8.85 to 8.92 (2H, d))

(3) Pig. Synthesis of -3:
0.6 g of (D-2) was added to 7 mL of phosphoric acid at room temperature, and then dissolved by heating to an internal temperature of 50 ° C. This solution was kept at an internal temperature of −2 to 0 ° C. under ice cooling, 0.24 g of sodium nitrite was added in portions, and the mixture was stirred at the same temperature for 1 hour to obtain a diazonium salt solution. Next, 0.6 g of the compound (Cp-1) separately obtained by the method of Synthesis Example 1 was suspended in 20 mL of methanol, and the prepared diazonium salt solution was added dropwise thereto at an internal temperature of 3 ° C. or lower. After stirring at the same temperature for 2 hours, the crystals formed by pouring into 50 mL of water were separated by filtration. Subsequently, the obtained crystals were added to 10 mL of methanol and 10 mL of water without drying, refluxed at 60 ° C. for 1 hour, and filtered at the same temperature. Furthermore, it wash | cleaned with 10 mL of methanol, and the obtained crystal | crystallization was dried at 60 degreeC for 3 hours, and 0.4g of specific examples (Pig.-3) of this invention were obtained.

[Synthesis Example 4] Synthesis of Exemplified Azo Pigment (Pig-4) The azo pigment (Exemplary Azo Pigment: Pig-4) of the present invention can be derived, for example, from the following synthetic route.

(1) Pig. Synthesis of -4:
1.0 g of (D-2) was added to 12 mL of phosphoric acid at room temperature, and then dissolved by heating to an internal temperature of 50 ° C. This solution was kept at an internal temperature of −3 to 0 ° C. under ice-cooling, 0.4 g of sodium nitrite was added in portions and stirred at the same temperature for 1 hour to obtain a diazonium salt solution. Next, 1.3 g of the compound (Cp-2) separately obtained by the method of Synthesis Example 2 was suspended in 26 mL of methanol, and the prepared diazonium salt solution was added dropwise thereto at an internal temperature of 3 ° C. or lower. After stirring for 1.5 hours at the same temperature, the crystals formed by pouring into 80 mL of water were separated by filtration. Subsequently, the obtained crystals were added to 40 mL of methanol and 20 mL of water without drying, refluxed at 60 ° C. for 1 hour, and filtered at the same temperature. The crystal obtained by washing with 20 mL of methanol was dried at 60 ° C. for 3 hours to obtain 1.4 g of a specific example (Pig.-4) of the present invention.

  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 mass.

[Example 1]
A planetary ball mill with 2.5 parts of the azo pigment (Pig-1) synthesized in Synthesis Example 1, 0.5 part of sodium oleate, 5 parts of glycerin, and 42 parts of water and 100 parts of zirconia beads having a diameter of 0.1 mm. Was used for dispersion for 6 hours at 300 rpm. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 1.

[Example 2]
5 parts of pigment (Pig-1) synthesized in Synthesis Example 1 and methacrylic acid-methacrylic acid ester copolymer represented by Dispersant Solution 10 described on page 22 of International Publication No. WO2006 / 064193 as a polymeric dispersant 25.5 parts of the combined aqueous solution and 19.5 parts of water were mixed and dispersed for 6 hours at 300 rpm with a planetary ball mill together with 100 parts of zirconia beads having a diameter of 0.1 mm. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 2.

[Example 3]
A yellow pigment dispersion 3 was obtained in the same manner as in Example 1 except that the specific compound example (Pig-2) of the present invention was used instead of the pigment (Pig-1) used in Example 1.

[Example 4]
A yellow pigment dispersion 4 was obtained in the same manner as in Example 1, except that the specific compound example (Pig-3) of the present invention was used instead of the pigment (Pig-1) used in Example 1.

[Example 5]
A yellow pigment dispersion 5 was obtained in the same manner as in Example 1 except that the specific compound example (Pig-4) of the present invention was used instead of the pigment (Pig-1) used in Example 1.

[Comparative Example 1]
Instead of the pigment (Pig-1) used in Example 1, C.I. I. A yellow comparative pigment dispersion 1 was obtained in the same manner as in Example 1 except that CI Pigment Yellow 128 (CROMOPHTAL YELLOW 8GN manufactured by Ciba Specialty) was used.

[Comparative Example 2]
Instead of the pigment (Pig-1) used in Example 1, C.I. I. A yellow comparative pigment dispersion 2 was obtained in the same manner as in Example 1 except that CI Pigment Yellow 74 (Iralite YELLOW GO manufactured by Ciba Specialty) was used.

[Comparative Example 3]
Instead of the pigment (Pig-1) used in Example 1, C.I. I. A yellow comparative pigment dispersion 3 was obtained in the same manner as in Example 1 except that CI Pigment Yellow 155 (INKJET YELLOW 4G VP2532 manufactured by Clariant) was used.

<Evaluation of coloring power>
The pigment dispersions obtained in the above Examples and Comparative Examples were No. No. 3 bar coater was applied to a photo mat paper <pigment only> manufactured by Seiko Epson Corporation. The image density of the obtained coated material was measured using a reflection densitometer (X-Rite 938 manufactured by X-Rite), and the results are shown in Table 1 as “coloring power (OD: Optical Density)”.

<Hue evaluation>
Regarding the hue, the chromaticity of the coating obtained as described above is ◯ (good) when it is visually less reddish and large in vividness, △ when one of them is not applicable, and △ when neither is applicable Evaluation was performed as x (defect).
The results are shown in Table 1.

<Light resistance evaluation>
The coated material having an image density of 1.0 used for hue evaluation was irradiated with xenon light (170000 lux; 325 nm or less in the presence of a cut filter) for 14 days using a fade meter, and the image density before and after the xenon irradiation was measured using a reflection densitometer. The pigment dispersions 1 to 5 and the comparative pigment dispersions 1 to 3 were evaluated as dye residual ratio [(concentration after irradiation / concentration before irradiation) × 100%]. The results are shown in Table 1.

  Accordingly, pigment dispersions using the pigments of the present invention include, for example, printing inks such as inkjets, color toners for electrophotography, displays such as LCDs and PDPs, and color filters and paints used in image sensors such as CCDs. It can be suitably used for colored plastics and the like.

2 is an infrared absorption spectrum diagram of an azo pigment 1 synthesized according to Synthesis Example 1. FIG. 5 is an infrared absorption spectrum diagram of an azo pigment 2 synthesized according to Synthesis Example 2. FIG. 6 is an infrared absorption spectrum diagram of an azo pigment 3 synthesized according to Synthesis Example 3. FIG. 6 is an infrared absorption spectrum diagram of an azo pigment 4 synthesized according to Synthesis Example 4. FIG.

Claims (8)

An azo pigment represented by the following general formula (1), a salt thereof, a hydrate, and a tautomer thereof.
General formula (1):

(In General Formula (1), R ₁ , P ₁ and Q ₁ each independently represents a hydrogen atom or a substituent. G constitutes an aromatic hydrocarbon ring in which a 5- to 6-membered heterocycle is condensed. W represents a substituent that can be bonded onto the aromatic hydrocarbon ring to which the heterocyclic ring that constitutes G is condensed, t represents an integer of 0 to 5. Het. 1 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 (1), and n is 1 to 1. It represents an integer of 3. When n = 2, it represents a dimer via R ₁ , P ₁ , Q ₁ , W, G or Het.1, and when n = 3, R ₁ , P ₁ , Represents a trimer via Q ₁ , W, G or Het.
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.) The azo pigment represented by the general formula (1) is an azo pigment represented by the following general formula (3), its azo pigment, its salt, hydrate, and them Tautomers of.
General formula (3):

(In General Formula (3), W ₁₁ , W ₁₂ , W ₁₃ , and R ₁ each independently represent a hydrogen atom or a substituent. G ′ is a 5- to 6-membered hetero ring that can be condensed to an aromatic hydrocarbon ring. Represents a non-metallic atomic group capable of constituting a ring, W represents a substituent which can be bonded to the heterocyclic ring formed by G ′, t represents an integer of 0 to 4. Het. The group chosen from the aromatic heterocyclic group group represented by general formula (2) of claim | item 1. represents * coupling | bonding with the azo group in general formula (3) in said general formula (2). N represents an integer of 1 to 3. When n = 2, it represents a dimer via R ₁ , W, W ₁₁ , W ₁₂ , W ₁₃ , G ′ or Het.1. (When n = 3, it represents a trimer via R ₁ , W, W ₁₁ , W ₁₂ , W ₁₃ , G ′ or Het.) The azo pigment represented by the general formula (1) or the general formula (3) is an azo pigment represented by the following general formula (4), Its salts, hydrates and their tautomers.
General formula (4):

(In the general formula (4), W ₁₁ , W ₁₂ , W ₁₃ , R ₁ , R ₂ and R ₃ each independently represent a hydrogen atom or a substituent. Het. 1 represents the general formula according to claim 1. Represents a group selected from the group of aromatic heterocyclic groups represented by (2), wherein * in the general formula (2) represents a bonding site with an azo group in the general formula (4); It represents an integer of ˜3, and when n = 2, it represents a dimer via R ₁ , R ₂ , R ₃ , W, W ₁₁ , W ₁₂ , W ₁₃ or Het. The case represents a trimer via R ₁ , R ₂ , R ₃ , W, W ₁₁ , W ₁₂ , W ₁₃ or Het. 1) The azo pigment represented by the general formula (1) or the general formula (3) is an azo pigment represented by the following general formula (5), Its salts, hydrates and their tautomers.
General formula (5):

(In the general formula (5), W ₁₁ , W ₁₂ , W ₁₃ , R ₁ , R ₂ and R ₃ each independently represents a hydrogen atom or a substituent. Het. 1 is the general formula according to claim 1. Represents a group selected from the group of aromatic heterocyclic groups represented by (2), wherein * in the general formula (2) represents a bonding site with an azo group in the general formula (5), and n represents 1. Represents an integer of ˜3, in the case of n = 2, it represents a dimer through R ₁ , R ₂ , R ₃ , W ₁₁ , W ₁₂ , W ₁₃ or Het. (Represents a trimer via R ₁ , R ₂ , R ₃ , W, W ₁₁ , W ₁₂ , W ₁₃ or Het.) In the azo pigments represented by the general formula (1), (3), (4) or the general formula (5), Het. The azo pigment according to any one of claims 1 to 4, wherein the aromatic heterocyclic group represented by -1 represents an aromatic heterocyclic group represented by the following general formula (6): Its salts, hydrates and their tautomers.
General formula (6):

(In General Formula (6), Y represents a hydrogen atom or a substituent. X represents an electron-withdrawing group having a Hammett's σp value of 0.2 or more. G ′ represents a 5- to 6-membered nitrogen-containing hetero group. This represents a group of nonmetallic atoms that can form a ring, and the heterocycle may be unsubstituted or substituted, and each heterocycle may be monocyclic or condensed. (* Represents a bonding site with an azo group.)   A pigment dispersion comprising at least one azo pigment according to any one of claims 1 to 5, a salt, a hydrate thereof, and a tautomer thereof.   A coloring composition comprising at least one of the azo pigment according to any one of claims 1 to 5, a salt, a hydrate thereof, and a tautomer thereof.   An ink for ink-jet recording comprising at least one of the azo pigment according to any one of claims 1 to 5, a salt, a hydrate thereof, and a tautomer thereof.

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