JP2010229177A - Azo compound, azo pigment, dispersion, coloring composition, and ink for inkjet recording - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an azo pigment and a pigment dispersion, which are excellent in chromatic characteristics such as a coloring power and a hue and are also excellent in durability such as light resistance. <P>SOLUTION: There are provided the azo compound represented by Formula (1), a tautomer thereof, and a salt or a hydrate thereof. In formula (1), R<SB>1</SB>to R<SB>3</SB>independently represent a hydrogen atom, a hydroxyl group, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carboxyl group, a carbamoyl group, an acylamino group, a sulfonamide group, a carbamoylamino group, a sulfamoyl group, an aliphatic oxy group, an aliphatic thio group, a cyano group, or a halogen atom, and do not together form any aromatic ring; R<SB>4</SB>represents an amino group or an aliphafic oxy group; A represents an aromatic 5- to 6-membered heterocyclic group; n represents an integer of 1 to 4; in the case of n=2, formula (1) represents a dimer through R<SB>1</SB>to R<SB>3</SB>or A; in the case of n=3, it represents a trimer through R<SB>1</SB>to R<SB>3</SB>or A; and in the case of n=4, Formula represents a tetramer through R<SB>1</SB>to R<SB>3</SB>or A provided that the azo compound represented by formula (1) does not include any form of a metal chelate pigment. <P>COPYRIGHT: (C)2011,JPO&INPIT

Description

  The present invention relates to a novel nitrogen-containing heterocyclic azo compound, an azo pigment, a dispersion containing the azo compound or an azo pigment, a coloring composition, 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 mixing method and subtractive color mixing method are used to display or record full color images. In fact, there is no fast-acting dye that has absorption characteristics that can realize the above-mentioned conditions and can withstand various use conditions and environmental conditions, and improvement is strongly desired.

The dyes and pigments used in each of the above applications must have the following properties in common. That is, it has preferable absorption characteristics in terms of color reproducibility, fastness under environmental conditions to be used, for example, light resistance, heat resistance, good resistance to oxidizing gases such as ozone, and the like. In addition, when the pigment is a pigment, it is substantially insoluble in water and organic solvents and has good chemical fastness, and even when used as particles, the preferred absorption characteristics in the molecular dispersion state are impaired. It is also necessary to have properties such as absence. The required characteristics can be controlled by the strength of intermolecular interaction, but it is difficult to achieve both because they are in a trade-off relationship.
In addition, when using the pigment, in addition to having a particle size and a particle shape necessary for expressing the desired transparency, fastness under the environmental conditions used, such as light resistance, heat resistance, Good resistance to oxidative gases such as ozone, and other chemical fastness to organic solvents and sulfurous acid gas. Disperse even fine particles in the medium used, and stable dispersion. , Etc. are also required. In particular, there is a strong demand for pigments that have a good 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 azo pigments are yellow diarylide pigments and red naphthol azo pigments. Examples of diarylide pigments include C.I. I. Pigment Yellow 12, 13 and 17 and the like. Examples of naphthol azo pigments include C.I. I. Pigment Red 208, 242 and the like. However, these pigments are extremely inferior in fastness, particularly light resistance, and are therefore not suitable for long-term storage of printed matter because the pigment is decomposed and faded when the printed matter is exposed to light.

  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 1 to 3). 3). However, even in the improved pigment, for example, the pigment described in Patent Document 1 has improved light resistance, but is still insufficient. For example, the pigment described in Patent Documents 2 and 3 has a green hue. There was a drawback that coloring power was lowered by taste and color characteristics were inferior.

  Patent Documents 4 to 6 disclose dyes having an absorption characteristic excellent in color reproducibility and sufficient fastness. However, the specific compounds described in the patent document have poor fastness even with good hue, poor hue even with good fastness, and are soluble in organic solvents and water. It is easy and the chemical fastness is not enough.

  When expressing a full color using a subtractive color mixing method of three colors of yellow, magenta, and cyan, or four colors including black, if a pigment with only one color inferior in color fastness is used, the printed gray If the balance is changed and a pigment having poor color characteristics is used, the color reproducibility at the time of printing is lowered. Therefore, in order to obtain a printed matter that maintains a high color reproducibility for a long period of time, a pigment and a pigment dispersion having both color characteristics and fastness are desired.

Conventionally, since azo dyes often have various visible light absorptions, they have been used as dyes in various fields. For example, it has come to be used in various fields such as coloring of synthetic resins, printing inks, dyes for sublimation thermal transfer materials, inkjet inks, and color filter dyes. An absorption spectrum is a large performance required for an azo dye as a dye. The hue of the pigment greatly affects the color and texture of an object colored by the pigment, and has a great effect on vision. Therefore, research on the absorption spectrum of dyes has been conducted for a long time.
Conventionally known azo dyes having a nitrogen-containing 5-membered ring as an azo component are also disclosed in Patent Documents 7 and 8. Although the dyes described in Patent Documents 7 and 8 have good dyes, the light fastness has never reached a high level, so further improvement is necessary.

  Patent Documents 4 and 9 disclose examples of bis-type azo dyes having chelate dyes and specific heterocyclic diazo components, but none satisfy the required performance in terms of image fastness and ink stability. It was.

JP-A-56-38354 U.S. Pat. No. 2,936,306 Japanese Patent Laid-Open No. 11-1000051 JP-A-1-191153 JP-A-10-58828 Japanese Patent Laid-Open No. 7-172059 JP-A-55-161856 JP 2008-7732 A JP-A-1-140166

  An object of the present invention is to provide an ink jet recording ink that is excellent in color characteristics such as tinting strength and hue, and can obtain an image having excellent durability such as light fastness, heat fastness, and ozone fastness. It is an object to provide an azo compound, an azo pigment, a dispersion, a coloring composition, and an ink for ink jet recording, which can improve ejection stability and ink liquid stability.

  As a result of extensive research, the present inventors have found that an ink liquid using a specific nitrogen-containing heterocyclic azo pigment has good ejection stability and ink liquid stability, and is resistant to light, heat and ozone. And obtained good robustness. Specific means for solving the above problems will be described below.

That is, the present invention
[1]
An azo compound represented by the following general formula (1), a tautomer thereof, a salt or a hydrate thereof.

(In the general formula (1), R _{1 to} R ₃ are each independently a hydrogen atom, a hydroxyl group, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carboxyl group, a carbamoyl group, or an acylamino group. , a sulfonamido group, a carbamoylamino group, a sulfamoyl group, an aliphatic oxy group, an aliphatic thio group, a cyano group or a halogen atom, but they do not form an aromatic ring bonded to each other .R ₄ is an amino group, fat Represents a heterocyclic group bonded with a group oxy group or a nitrogen atom, A represents an aromatic 5- to 6-membered heterocyclic group, n represents an integer of 1 to 4, and when n = 2, R _{1 to} R Represents a dimer via ₃ or A. When n = 3, it represents a trimer via R _{1 to} R ₃ or A. When n = 4, it represents a R _{1 to} R ₃ or A. Represents a tetramer, provided that the general formula (1 The azo compound represented by) does not include a metal chelate dye form.)

[2]
In the azo compound represented by the general formula (1), A is represented by any one of the following general formulas (A-1) to (A-30): Compound, its tautomer, salt or hydrate thereof.

(In the general formulas (A-1) to (A-30), R _{51 to} R ₅₈ each independently represent a hydrogen atom or a substituent, and the adjacent substituents are bonded to each other to form a 5- to 6-membered ring. R ₅₉ represents a substituent, and adjacent substituents may be bonded to each other to form a 5- to 6-membered ring, and R ₆₀ and R ₆₁ are each independently a hydrogen atom. Or represents a substituent, * represents a bonding position with the azo group of the general formula (1).

[3]
An azo pigment represented by the following general formula (1), a tautomer thereof, a salt or a hydrate thereof.

(In the general formula (1), R _{1 to} R ₃ are each independently a hydrogen atom, a hydroxyl group, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carboxyl group, a carbamoyl group, or an acylamino group. , a sulfonamido group, a carbamoylamino group, a sulfamoyl group, an aliphatic oxy group, an aliphatic thio group, a cyano group or a halogen atom, but they do not form an aromatic ring bonded to each other .R ₄ is an amino group, fat Represents a heterocyclic group bonded with a group oxy group or a nitrogen atom, A represents an aromatic 5- to 6-membered heterocyclic group, n represents an integer of 1 to 4, and when n = 2, R _{1 to} R Represents a dimer via ₃ or A. When n = 3, it represents a trimer via R _{1 to} R ₃ or A. When n = 4, it represents a R _{1 to} R ₃ or A. Represents a tetramer, provided that the general formula (1 The azo pigment represented by) does not include the form of a metal chelate dye.)

[4]
In the azo pigment represented by the general formula (1), A is represented by any one of the general formulas (A-1) to (A-30). , Tautomers thereof, salts or hydrates thereof.

(In the general formulas (A-1) to (A-30), R _{51 to} R ₅₈ each independently represents a hydrogen atom or a substituent, and adjacent substituents are bonded to each other to form a 5- to 6-membered ring. R ₅₉ represents a substituent, and adjacent substituents may be bonded to each other to form a 5- to 6-membered ring, and R ₆₀ and R ₆₁ are each independently a hydrogen atom. Or represents a substituent, * represents a bonding position with the azo group of the general formula (1).

[5]
The azo pigment represented by the general formula (1) is represented by the following general formula (2), the azo pigment according to [4], a tautomer thereof, a salt or hydration thereof object.

(In General Formula (2), R _{21 to} R ₂₃ are each independently a hydrogen atom, a hydroxyl group, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carboxyl group, a carbamoyl group, or an acylamino group. , a sulfonamido group, a carbamoylamino group, a sulfamoyl group, an aliphatic oxy group, an aliphatic thio group, a cyano group or a halogen atom, bonded to each other .R ₂₄ but they do not form an aromatic ring is a hydrogen atom, the total An alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heterocyclic group having 2 to 12 carbon atoms in total, which may be saturated or unsaturated, A ₂ Is represented by any of the above general formulas (A-10) to (A-30), n represents an integer of 1 to 4. When n = 2, R _{21 to} R ₂₃ or A ₂ is represented by Represents a dimer via For n = 3 in the case of .n = 4 representing a trimer formed through _R 21 _{to R 23} or _{A 2} represents a tetramer formed through _R 21 _{to R 23} or _{A 2.)}

[6]
A dispersion containing at least one azo compound according to [1] or [2] or an azo pigment according to any one of [3] to [5].

[7]
A coloring composition comprising at least one of the azo compound according to [1] or [2] or the azo pigment according to any one of [3] to [5].

[8]
[7] An ink for inkjet recording, comprising the dispersion described in [7].

  The present invention relates to an azo compound, an azo pigment, a dispersion, a coloring composition, and an ink for inkjet recording, and has excellent color characteristics such as coloring power and hue, and light fastness, heat fastness, and ozone fastness. Such an image having excellent durability can be obtained, and when used as an ink for inkjet recording, the ejection stability and the ink liquid stability are excellent. In particular, it is optimal as a novel ink-jet pigment ink containing an azo pigment.

It is a figure of the infrared absorption spectrum of specific compound example D-51 synthesize | combined according to the synthesis example 1. FIG. It is a figure of the infrared absorption spectrum of specific compound example D-52 synthesize | combined according to the synthesis example 2. FIG. It is a figure of the infrared absorption spectrum of specific compound example D-53 synthesize | combined according to the synthesis example 3. FIG.

First, the aliphatic group, aryl group, heterocyclic group and substituent in the present invention will be described.
In the aliphatic group in the present invention, the aliphatic moiety may be linear, branched or cyclic. Moreover, it may be saturated or unsaturated. Specific examples include an alkyl group, an alkenyl group, a cycloalkyl group, and a cycloalkenyl group. Furthermore, the aliphatic group may be unsubstituted or may have a substituent.

  The aryl group may be a single ring or a condensed ring. Further, it may be unsubstituted or may have a substituent. Moreover, the heterocyclic group should just have a hetero atom (for example, a nitrogen atom, a sulfur atom, an oxygen atom) in the ring, and even if it is a saturated ring, it is an unsaturated ring. Also good. Further, it may be a single ring or a condensed ring, and may be unsubstituted or have a substituent.

  Further, the substituent in the present invention may be any group that can be substituted. For example, an aliphatic group, an aryl group, a heterocyclic group, an acyl group, an acyloxy group, an acylamino group, an aliphatic oxy group, an aryloxy group, a hetero group Ring oxy group, aliphatic oxycarbonyl group, aryloxycarbonyl group, heterocyclic oxycarbonyl group, carbamoyl group, aliphatic sulfonyl group, arylsulfonyl group, heterocyclic sulfonyl group, aliphatic sulfonyloxy group, arylsulfonyloxy group, hetero Ring sulfonyloxy group, sulfamoyl group, aliphatic sulfonamide group, aryl sulfonamide group, heterocyclic sulfonamide group, amino group, aliphatic amino group, arylamino group, heterocyclic amino group, aliphatic oxycarbonylamino group, aryl Oxycarbonylamino group, heterocycle Xoxycarbonylamino group, aliphatic sulfinyl group, arylsulfinyl group, aliphatic thio group, arylthio group, hydroxy group, cyano group, sulfo group, carboxy group, aliphatic oxyamino group, aryloxyamino group, carbamoylamino group, sulfo group Famoylamino group, halogen atom, sulfamoylcarbamoyl group, carbamoylsulfamoyl group, dialiphatic oxyphosphinyl group, diaryloxyphosphinyl group, ionic hydrophilic group (for example, carboxyl group, sulfo group, Phosphono group and quaternary ammonium group).

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

Here, Hammett's substituent constant σp value used in the present specification will be described briefly.
Hammett's rule is a method described in 1935 in order to quantitatively discuss 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, but this means that it is limited to only a substituent having a value known in the literature, which can be found in the above-mentioned book. Needless to say, even if the value is unknown, it includes a substituent that would be included in the range when measured based on Hammett's rule. Although the compound represented by the general formula (1) or (2) of the present invention is not a benzene derivative, 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.

  The azo compound of the present invention is represented by the following general formula (1).

  Hereinafter, the compound represented by the general formula (1) will be described.

(In General Formula (1), R _{1 to} R ₃ each independently have a hydrogen atom, a hydroxyl group, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carboxyl group, or a substituent. Carbamoyl group, acylamino group, sulfonamide group, carbamoylamino group optionally having substituent, sulfamoyl group optionally having substituent, aliphatic oxy group, aliphatic thio group, cyano R ₄ represents an amino group, an aliphatic oxy group, or a hetero ring group bonded by a nitrogen atom, and A represents an aromatic 5- Represents a 6-membered heterocycle, n represents an integer of 1 to 4. When n = 2, it represents a dimer via R _{1 to} R ₃ or A. When n = 3, R _{1 to} R Represents a trimer via ₃ or A. When n = 4, it represents a tetramer via R _{1 to} R ₃ or A. However, the azo compound represented by the general formula (1) does not include a form of a metal chelate dye.

From the viewpoint of image fastness, R ₁ is preferably a hydrogen atom, a hydroxyl group, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, or a sulfonamide group. , An aliphatic oxy group, a cyano group or a halogen atom, R ₂ may have a hydrogen atom, a hydroxyl group, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carboxyl group, or a substituent. Carbamoyl group, acylamino group, sulfonamide group, carbamoylamino group which may have a substituent, sulfamoyl group which may have a substituent, aliphatic oxy group, aliphatic thio group, cyano group or halogen atom , R ₃ is a hydrogen atom, a hydroxyl group, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, substituted Carbamoyl group, a sulfonamido group, sulfamoyl group optionally having a substituent, a cyano group or a halogen atom, more preferably R ₁ is a hydrogen atom, a hydroxyl group, an aliphatic group, an aliphatic oxycarbonyl group, Optionally substituted carbamoyl group, aliphatic oxy group, cyano group or halogen atom, R ₂ has a hydrogen atom, aliphatic group, heterocyclic group, aliphatic oxycarbonyl group, or substituent. A carbamoyl group, a carboxyl group, an aliphatic oxy group, a cyano group or a halogen atom, R ₃ may be a hydrogen atom, an aliphatic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, a cyano group or a halogen atom. Most preferably R ₁ is a hydrogen atom and R ₂ is a hydrogen atom, an aliphatic oxycarbonyl group or a substituent. It is a carbamoyl group which may have, and R ₃ is a hydrogen atom.

The aliphatic group represented by R ₁ to R ₃ may have a substituent, may be saturated or unsaturated, and examples of the group that may be substituted include the above-described substituents. Any group can be used as long as it is a substitutable group among the groups described in the group section. The aliphatic group of R ₁ to R ₃ is preferably an alkyl group having 1 to 8 carbon atoms, more preferably an alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, i-propyl. , Cyclohexyl, t-butyl and the like.

The aryl group represented by R ₁ to R ₃ may have a substituent, and the group that may be substituted is a group that can be substituted with a group that can be substituted with the groups described in the above-mentioned substituents section. Anything is fine. The aryl group of R ₁ to R ₃ is preferably an aryl group having 6 to 12 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms, such as phenyl, 3-methoxyphenyl, 4 -Carbamoylphenyl and the like.

The heterocyclic group represented by R ₁ to R ₃ may have a substituent, may be saturated or unsaturated, may be condensed, or may be substituted. As the good group, any group can be used as long as it is a group that can be substituted with the groups described in the section of the substituent. The heterocyclic group of R ₁ to R ₃ is preferably a heterocyclic group having 2 to 16 carbon atoms in total, more preferably a 5 to 6-membered heterocyclic group having 2 to 12 carbon atoms in total, For example, 1-pyrrolidinyl, 4-morpholinyl, 2-pyridyl, 1-pyrrolyl, 1-imidazolyl, 1-benzoimidazolyl and the like can be mentioned.

The aliphatic oxycarbonyl group represented by R ₁ to R ₃ may have a substituent, may be saturated or unsaturated, and examples of the group that may be substituted include those described above. Any group can be used as long as it is a group that can be substituted with the groups described in the section of the substituent. The aliphatic oxycarbonyl group of R ₁ to R ₃ is preferably an alkoxycarbonyl group having 1 to 8 carbon atoms in total, more preferably an alkoxycarbonyl group having 1 to 6 carbon atoms in total, such as methoxycarbonyl, i-propyloxycarbonyl, carbamoylmethoxycarbonyl and the like can be mentioned.

The carbamoyl group represented by R ₁ to R ₃ may have a substituent, and the group that may be substituted is a group that can be substituted with the group described in the above-mentioned substituent group, or a substitutable group. Any group may be used, and an aliphatic group, an aryl group, a heterocyclic group and the like are preferable. The carbamoyl group optionally having a substituent of R ₁ to R ₃ is preferably a carbamoyl group, an alkylcarbamoyl group having 2 to 9 carbon atoms in total, a dialkylcarbamoyl group having 3 to 10 carbon atoms in total, or a total carbon An arylcarbamoyl group having 7 to 13 atoms and a heterocyclic carbamoyl group having 3 to 12 carbon atoms, more preferably a carbamoyl group, an alkylcarbamoyl group having 2 to 7 carbon atoms, and 3 to 6 carbon atoms. Dialkylcarbamoyl groups, arylcarbamoyl groups having 7 to 11 carbon atoms in total, and heterocyclic carbamoyl groups having 3 to 10 carbon atoms in total, such as carbamoyl, methylcarbamoyl, dimethylcarbamoyl, phenylcarbamoyl, 4-pyridinecarbamoyl, etc. Is mentioned.

The acylamino group represented by R ₁ to R ₃ may have a substituent, and may be aliphatic, aromatic, heterocyclic, or substituted. As a good group, any group can be used as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. The acylamino group of R ₁ to R ₃ is preferably an acylamino group having 2 to 12 carbon atoms in total, more preferably an acylamino group having 1 to 8 carbon atoms in total, and still more preferably 1 to 1 carbon atoms in total. 8 alkylcarbonylamino groups such as acetylamino, benzoylamino, 2-pyridinecarbonylamino, propanoylamino and the like.

The sulfonamide group represented by R ₁ to R ₃ may have a substituent, and may be aliphatic, aromatic, heterocyclic, or substituted. As the good group, any group can be used as long as it is a group which can be substituted with the groups described in the above-mentioned substituent group. The sulfonamide group of R ₁ to R ₃ is preferably a sulfonamide group having 1 to 12 carbon atoms, more preferably a sulfonamide group having 1 to 8 carbon atoms, and still more preferably a total carbon atom. Examples of the alkylsulfonamide group having 1 to 8 include methanesulfonamide, benzenesulfonamide, and 2-pyridinesulfonamide.

The carbamoylamino group represented by R ₁ to R ₃ may have a substituent, and the group that may be substituted includes a group that can be substituted with the groups described in the above-mentioned substituents section. As long as it is an aliphatic group, an aryl group, a heterocyclic group, or the like. The carbamoylamino group which may have a substituent of R ₁ to R ₃ is preferably a carbamoylamino group, an alkylcarbamoylamino group having 2 to 9 carbon atoms in total, and a dialkylcarbamoylamino having 3 to 10 carbon atoms in total. Group, an arylcarbamoylamino group having 7 to 13 carbon atoms in total, and a heterocyclic carbamoylamino group having 3 to 12 carbon atoms in total, more preferably a carbamoylamino group and an alkylcarbamoylamino group having 2 to 7 carbon atoms in total. A dialkylcarbamoylamino group having 3 to 6 carbon atoms, an arylcarbamoylamino group having 7 to 11 carbon atoms, and a heterocyclic carbamoylamino group having 3 to 10 carbon atoms, such as carbamoylamino and methylcarbamoyl Amino, N, N-dimethylcarbamoylamino, phenylcarbamo Arylamino, 4-pyridine carbamoylamino, and the like.

The sulfamoyl group represented by R ₁ to R ₃ may have a substituent, and the group that may be substituted may be any group that can be substituted with the groups described in the above-mentioned substituents section. Any may be used, and an aliphatic group, an aryl group, a heterocyclic group and the like are preferable. The sulfamoyl group optionally having a substituent of R ₁ to R ₃ is preferably a sulfamoyl group, an alkylsulfamoyl group having 1 to 9 carbon atoms in total, and a dialkylsulfamoyl group having 2 to 10 carbon atoms in total. Group, an arylsulfamoyl group having 7 to 13 carbon atoms in total, and a heterocyclic sulfamoyl group having 2 to 12 carbon atoms in total, more preferably a sulfamoyl group and an alkylsulfamoyl group having 1 to 7 carbon atoms in total. A dialkylsulfamoyl group having 3 to 6 carbon atoms, an arylsulfamoyl group having 6 to 11 carbon atoms, and a heterocyclic sulfamoyl group having 2 to 10 carbon atoms, such as sulfamoyl, Famoyl, N, N-dimethylsulfamoyl, phenylsulfamoyl, 4-pyridinesulfamoyl and the like can be mentioned.

The aliphatic oxy group represented by R ₁ to R ₃ may have a substituent, may be saturated or unsaturated, and may be substituted. Any group can be used as long as it is a group that can be substituted among the groups described in the section of the substituent. The aliphatic oxy group of R ₁ to R ₃ is preferably an alkoxy group having 1 to 8 carbon atoms in total, more preferably an alkoxy group having 1 to 6 carbon atoms in total, such as methoxy, ethoxy, i- Examples include propyloxy, cyclohexyloxy, methoxyethoxy and the like.

The aliphatic thio group represented by R ₁ to R ₃ may have a substituent, may be saturated or unsaturated, and may be substituted. Any group can be used as long as it is a group that can be substituted among the groups described in the section of the substituent. The aliphatic thio group of R ₁ to R ₃ is preferably an alkylthio group having 1 to 8 carbon atoms, more preferably an alkylthio group having 1 to 6 carbon atoms. For example, methylthio, ethylthio, carbamoylmethylthio , T-butylthio and the like.

The halogen atom represented by R ₁ to R ₃ is preferably a fluorine atom, a chlorine atom or a bromine atom, more preferably a chlorine atom.

Among R ₁ to R ₃ , the number of groups other than hydrogen atoms is preferably 0 to 2, more preferably 0 to 1, and even more preferably 0. n represents an integer of 1 to 4. Particularly preferably, n = 1 to 3, of which n is preferably 1 or 2, and most preferably n = 1.

From the viewpoint of color characteristics, R ₄ is preferably an amino group which may have a substituent, an aliphatic oxy group, or a saturated heterocyclic group bonded with a nitrogen atom, and more preferably a substituent. An amino group which may have

The amino group represented by R ₄ may have a substituent, and the group that may be substituted may be any of the groups described in the above-mentioned substituent group and may be substituted. Any substituent may be used, and preferred examples of the substituent include an aliphatic group, an aryl group, and a heterocyclic group. As the amino group which may have a substituent represented by R ₄ , an unsubstituted amino group, an alkylamino group having 1 to 10 carbon atoms in total, a dialkylamino group having 2 to 10 carbon atoms in total, An arylamino group having 6 to 12 carbon atoms in total, a heterocyclic amino group which may be saturated or unsaturated having 2 to 12 carbon atoms in total, more preferably an unsubstituted amino group, Even if the alkylamino group having 1 to 8 carbon atoms, the dialkylamino group having 2 to 8 carbon atoms, the arylamino group having 6 to 10 carbon atoms, or the saturation having 2 to 12 carbon atoms, A heterocyclic amino group which may be unsaturated, for example, methylamino, N, N-dimethylamino, N-phenylamino, N- (2-pyrimidyl) amino and the like.

The aliphatic oxy group represented by R ₄ may have a substituent, and the substituent is the group described in the above-mentioned substituent group, and any substituent can be used. Good. The aliphatic oxy group for R ₄ is preferably an alkoxy group having 1 to 8 carbon atoms in total, more preferably an alkoxy group having 1 to 4 carbon atoms in total, such as methoxy, ethoxy, (t) -Butoxy, methoxyethoxy, carbamoylmethoxy and the like.

The heterocyclic group represented by R ₄ may be a saturated heterocyclic ring or an unsaturated heterocyclic group, and may have a substituent. Examples of the substituent include the substituents described above. Any group may be used as long as it is a group that can be substituted. The heterocyclic group of R ₁ is preferably a heterocyclic group having 2 to 10 carbon atoms in total, more preferably a saturated heterocyclic group bonded with a nitrogen atom having 2 to 8 carbon atoms in total, for example, Examples include 1-piperidyl, 4-morpholinyl, 2-pyrimidyl, 4-pyridyl and the like.

  The aromatic 5- to 6-membered heterocycle represented by A may be condensed or monocyclic, the condensed ring may be a hydrocarbon ring, and the condensed ring is a hydrocarbon ring. Or a hetero ring, an aromatic ring, or a non-aromatic ring, preferably an aromatic 5- to 6-membered ring containing 1 to 3 heteroatoms. . The aromatic 5- to 6-membered heterocyclic ring which may be condensed is preferably 2 to 15 carbon atoms, preferably 2 to 10 carbon atoms, such as a pyridine ring or pyrazine. Ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, isoxazole ring, isothiazole ring, triazole ring, thiadiazole ring, oxadiazole ring And the like, and a condensed heterocyclic group of them with a benzene ring derivative or a heterocyclic derivative, and more preferably, as a single ring, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, a triazine ring, a pyrrole ring, a furan ring Thiophene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, isoxazole , An isothiazole ring, a triazole ring, a thiadiazole ring, an oxadiazole ring, and a condensed ring, for example, without specifying the position and position of the condensed ring, it was condensed with a substituted or unsubstituted benzene ring Pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, thiazole ring, isoxazole ring, isothiazole ring, triazole ring, thiadiazole ring, oxadiazole Among them, a pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, isoxazole as a single ring among them. Ring, isothiazole ring, triazole A ring, a thiadiazole ring and an oxadiazole ring are preferable, and a pyrazole ring as a monocyclic ring is most preferable.

  In the azo compound represented by the general formula (1), A is preferably an azo compound represented by the following general formulas (A-1) to (A-30).

(In the general formulas (A-1) to (A-30), R _{51 to} R ₅₈ each independently represent a hydrogen atom or a substituent, and adjacent substituents are bonded to each other to form a 5- to 6-membered ring. R ₅₉ represents a substituent, and adjacent substituents may be bonded to each other to form a 5- to 6-membered ring, and R ₆₀ and R ₆₁ are each independently a hydrogen atom. Or represents a substituent, * represents a bonding position with the azo group of the general formula (1).

  General formulas (A-1) to (A-30) represented by A will be described.

The substituent represented by R _{51 to} R ₅₄ may be any group as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. However, in the general formula (A-1), when R ₅₃ is a hydroxyl group and R ₅₄ is an amino group, it is not preferable from the viewpoint of hue, and is excluded. As the substituent, from the viewpoint of hue, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an acylamino group, a sulfonamide group, an aliphatic oxy Group, an aliphatic thio group, a cyano group, etc., particularly preferably an aliphatic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an aliphatic oxy group, a cyano group, etc. A carbamoyl group which may have a substituent and a cyano group are preferable.

As the substituent represented by R ₅₅ and R ₅₉ , any group can be used as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. From the viewpoint of the effect of the present invention, the substituent of R ₅₅ and R ₅₉ is preferably an aliphatic group, an aryl group, a heterocyclic group, etc., particularly preferably an aliphatic group, an aryl group, or a position adjacent to the binding site. An aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom is most preferred, and an aromatic 5- to 6-membered heterocyclic group containing a nitrogen atom at the adjacent position of the binding site is most preferred. R ₅₅ and R ₅₉ are aromatic 5- to 6-membered heterocyclic groups containing a nitrogen atom adjacent to the binding site, thereby strengthening not only intermolecular interactions of dye molecules but also intramolecular interactions Easy to form. This makes it easy to construct a pigment having a stable molecular arrangement, which is preferable in terms of showing good hue and high fastness (light resistance, gas, heat, water, etc.).

As the substituent represented by R ₅₆ , R ₅₇ , R ₆₀ , R ₆₁ , any group can be used as long as it is a group that can be substituted with the groups described in the above-mentioned substituents section. As a substituent for R ₅₆ , R ₅₇ , R ₆₀ and R _61, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, an optionally substituted carbamoyl group, an acylamino group, A sulfonamide group, an aliphatic oxy group, an aliphatic thio group, a cyano group, etc., particularly preferably an aliphatic group, an aliphatic oxy group, an optionally substituted carbamoyl group, an aliphatic thio group, a cyano group; And the most preferable are a carbamoyl group which may have a substituent, and a cyano group.

The substituent represented by R ₅₈ may be any group as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. In view of the effect of the present invention, R ₅₈ is preferably a heterocyclic group or an electron-withdrawing group having Hammett's substituent constant σp value of 0.2 or more, and σp value of 0.3 or more. It is preferably an attractive group. The upper limit is 1.0 or less electron withdrawing group.

Specific examples of R ₅₈ which is an electron-attracting group having a σp value of 0.2 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group, dialkylphosphonic group Group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, alkyl halide Groups, 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 0.2 or more, heterocyclic groups, Halogen atom, azo group, or selenasia Include the over door group.

In A of the general formula (1), R ₅₅ is preferably any of the following (Y-1) to (Y-13), and any of the following (Y-1) to (Y-6) Is more preferable, and the following (Y-1), (Y-4) or (Y-6) is more preferable. * In the general formulas (Y-1) to (Y-13) represents a bonding site with the N atom of the heterocyclic ring. Y _{1 to} Y ₁₁ each independently represent a hydrogen atom or a substituent. G ₁₁ in (Y-13) represents a nonmetallic atom group that can form a 5- to 6-membered heterocycle, and the heterocycle represented by G ₁₁ has a substituent even if it is unsubstituted. The heterocycle may be monocyclic or condensed. Formulas (Y-1) to (Y-13) may have tautomeric structures together with substituents.

In the compound represented by the general formula (1), from the viewpoint of image fastness, the number of groups other than a hydrogen atom among R ₁ to R ₃ is 0 or 1, and the substituent is an aliphatic oxycarbonyl group Or a carbamoyl group which may have a substituent, wherein R ₄ is an amino group which may have a substituent, and A is (A-10) to (A-18), ( Any one of A-20), (A-22) to (A-26), and (A-28), and n is preferably 1 or 2, and any one of R ₁ to R ₃ other than a hydrogen atom The number of the group is 0, and R ₄ is an amino group which may have a substituent, and A is (A-10) to (A-20), (A-22) to (a-26), there is (a-28) either, more preferably n represents 1 or 2, hydrogen atoms of from _{R 1 R 3} or less A number that is of the group is 0, an amino group which may _{R 4} is substituted, A is, (A-10), ( A-15) ~ (A-17), (A-20) or (A-28), wherein n is 1 or 2 is more preferable, and the number of groups other than a hydrogen atom among R ₁ to R ₃ is 0. , R ₄ is an amino group which may have a substituent, and A is (A-16) and n is preferably 1 or 2, and particularly when n = 1 preferable.

As a preferable combination of R ₅₈ , R ₅₈ and R ₅₈ in formula (A-16), R ₅₈ is an acyl group, a carbamoyl group, an alkyloxycarbonyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an alkoxysulfonyl group. Or a sulfamoyl group, wherein R ₅₆ is a hydrogen atom or an aliphatic group having 1 to 12 carbon atoms in total, and R ₅₅ is a 5- to 6-membered aromatic group containing a nitrogen atom adjacent to the binding site The case where it is a heterocyclic group is preferable.
R ₅₈ is a carbamoyl group, an alkyloxycarbonyl group or a cyano group, R ₅₆ is a hydrogen atom or an aliphatic group, and R ₅₅ is any one of (Y-1) to (Y-13). Some cases are preferred.
In particular, R ₅₈ is preferably a carbamoyl group or a cyano group, R ₅₆ is a hydrogen atom or an aliphatic group, and R ₅₅ is any one of (Y-1) to (Y-6).
Among them, it is most preferable that R ₅₈ is a cyano group, R ₅₆ is a hydrogen atom, and R ₅₅ is any one of (Y-1), (Y-4), and (Y-6). .

<Azo pigment>
A pigment is a state in which molecules are firmly bonded to each other by cohesive energy due to strong interaction between dye molecules. In order to create this state, it is described in, for example, Journal of Imaging Society of Japan, Vol. 43, page 10 (2004) that van der Waals force between molecules and hydrogen bonding between molecules are necessary.
In order to increase the van der Waals force between molecules, introduction of an aromatic group, a polar group and / or a hetero atom into the molecule can be considered. Moreover, in order to form an intermolecular hydrogen bond, introduction | transduction of the substituent containing the hydrogen atom couple | bonded with the hetero atom to a molecule | numerator and / or introduction | transduction of an electron-donating ring-setting group etc. can be considered. Further, it is considered preferable that the polarity of the whole molecule is high. For this purpose, for example, a shorter chain group such as an alkyl group is preferred, and a smaller molecular weight / azo group value is preferred.
From these viewpoints, the pigment molecule preferably contains an amide bond, a sulfonamide bond, an ether bond, a sulfone group, an oxycarbonyl group, an imide group, a carbamoylamino group, a hetero ring, a benzene ring and the like.

The present invention also relates to an azo pigment represented by the general formula (1), a tautomer thereof, a salt or a hydrate thereof.
The compound represented by the general formula (1) can easily form an intermolecular interaction of dye molecules due to its specific structure, has low solubility in water or an organic solvent, and can be an azo pigment.
A pigment is used by being finely dispersed as solid particles such as molecular aggregates in a solvent, unlike a dye used by being dissolved in water or an organic solvent in a molecular dispersion state.
In addition, by having a specific structure represented by the following general formula (1), it exhibits excellent characteristics in color characteristics such as coloring power and hue, and is excellent in durability such as light resistance and ozone resistance. Characteristics can be shown.

(In General Formula (1), R _{1 to} R ₃ each independently have a hydrogen atom, a hydroxyl group, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carboxyl group, or a substituent. Carbamoyl group, acylamino group, sulfonamide group, carbamoylamino group optionally having substituent, sulfamoyl group optionally having substituent, aliphatic oxy group, aliphatic thio group, cyano R ₄ represents an amino group, an aliphatic oxy group, or a hetero ring group bonded by a nitrogen atom, and A represents an aromatic 5- Represents a 6-membered heterocycle, n represents an integer of 1 to 4. When n = 2, it represents a dimer via R _{1 to} R ₃ or A. When n = 3, R _{1 to} R Represents a trimer via ₃ or A. When n = 4, it represents a tetramer through R _{1 to} R ₃ or A. However, the azo pigment represented by the general formula (1) does not include a form of a metal chelate dye.

  Examples of the substituents of the azo pigment represented by the general formula (1) and preferred combinations of the substituents are the same as those described for the azo compound represented by the general formula (1).

  In the azo pigment represented by the general formula (1), A is preferably represented by the following general formulas (A-1) to (A-30).

  In the azo pigment represented by the general formula (1), examples of the substituent groups represented by the general formulas (A-1) to (A-30) and preferred combinations of substituents are represented by the general formula (1). The same as those mentioned for the azo compound.

The azo pigment represented by the general formula (1) is particularly preferably an azo pigment represented by the following general formula (2).

(In the general formula (2), R _{21 to} R ₂₃ each independently have a hydrogen atom, a hydroxyl group, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carboxyl group, or a substituent. Carbamoyl group, acylamino group, sulfonamide group, carbamoylamino group optionally having substituent, sulfamoyl group optionally having substituent, aliphatic oxy group, aliphatic thio group, cyano R ₂₄ represents a hydrogen atom, an alkyl group having 1 to 8 carbon atoms in total, an aryl group having 6 to 10 carbon atoms in total, or a total carbon atom. Represents a heterocyclic group which may be saturated or unsaturated with 2 to 12 atoms, and A ₂ is represented by any one of the general formulas (A-10) to (A-30). N is 1-4 For .n = 2 represents an _integer, in the case of .n = 3 representing a dimer formed through R 21 _{to R 23} or _{A 2} represents a trimer formed through _R 21 _{to R 23} or _{A 2} (When n = 4, it represents a tetramer via R _{21 to} R ₂₃ or A ₂ )

R < ₂₁ > -R < ₂₃ > in the said General formula (2) is synonymous with R < ₁ > -R < ₃ > in General formula (1) respectively, A preferable example is also the same.

The alkyl group having 1 to 8 carbon atoms in total represented by R ₂₄ may have a substituent, and the substituent is a group that can be substituted with the group described in the above-mentioned substituent section. Anything is acceptable. The alkyl group having 1 to 8 carbon atoms in total represented by R ₂₄ is preferably an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl, (s) -butyl, methoxyethyl, carbamoylmethyl. Etc.

The aryl group having 6 to 10 carbon atoms in total represented by R ₂₄ may have a substituent, and the substituent is a group that can be substituted with the group described in the above-mentioned substituent group. Anything is acceptable. Examples of the aryl group having 6 to 10 carbon atoms in total represented by R ₂₄ include phenyl, 3-methoxyphenyl, 4-carbamoylphenyl and the like.

As the heterocyclic group which may be saturated or unsaturated having 2 to 12 carbon atoms in total represented by R ₂₄ , the substituent may be the group described in the above-mentioned substituent group, Any group that can be substituted is acceptable. The heterocyclic group represented by R ₂₄ which may be saturated or unsaturated having 2 to 12 carbon atoms in total is preferably a 5- to 6-membered heterocyclic ring having 2 to 12 carbon atoms in total. Groups such as 1-pyrrolidinyl, 4-morpholinyl, 2-pyridyl, 1-pyrrolyl, 1-imidazolyl, 1-benzimidazolyl and the like.

In the pigment represented by the general formula (2), from the viewpoint of image fastness, the number of groups other than a hydrogen atom among R ₂₁ to R ₂₃ is 0 or 1, and the substituent is an aliphatic oxycarbonyl group Or a carbamoyl group which may have a substituent, wherein R ₂₄ is an amino group which may have a substituent, and A is (A-10) to (A-18), ( Any one of A-20), (A-22) to (A-26), and (A-28), and n is preferably 1 or 2, and any one of R ₂₁ to R ₂₃ other than a hydrogen atom The number of the group is 0, and R ₂₄ is an amino group which may have a substituent, and A is (A-10) to (A-20), (A-22) to (a-26), be either (a-28), more preferably n represents 1 or _2, the _{R 21} of _{R 23} The number is a non-Chi hydrogen atom of the group is _0, an amino group which may _{R 24} is substituted, A is, (A-10), ( A-15) ~ (A -17), (A-20), or (A-28), wherein n is 1 or 2, and the number of R ₂₁ to R ₂₃ which is a group other than a hydrogen atom is more preferable. Most preferably, it is 0, R ₂₄ is an amino group which may have a substituent, A is (A-16), and n is 1 or 2.

  In terms of the effects of the present invention, the compound and pigment represented by the general formula (1) preferably have “total carbon number / number of azo groups” of 40 or less, and more preferably 30 or less. In terms of the effects of the present invention, the compound and pigment represented by the general formula (1) preferably have a “molecular weight / number of azo groups” of 700 or less. From the viewpoint of the effect of the present invention, the compound represented by the general formula (1) and the pigment are preferably not substituted with an ionic substituent such as a sulfo group or a carboxyl group.

The present invention includes within its scope tautomers of the azo compound represented by the general formula (1) and the pigment.
The general formula (1) is shown in the form of an extreme structural formula among several tautomers that can be taken in terms of chemical structure, but may be a tautomer other than the structure described, You may use as a mixture containing these tautomers.
For example, for the azo compound and pigment represented by the general formula (1), an azo-hydrazone tautomer represented by the following general formula (1 ′) can be considered.
The present invention includes in its scope the compound represented by the following general formula (1 ′), which is a tautomer of the azo compound represented by the general formula (1) and the pigment.

In general formula (1 ′), R _{1 to} R ₄ , A, and n are the same as those defined in general formula (1).

  Among the azo compounds and pigments represented by the general formula (1), examples of particularly preferred azo compounds and pigments are represented by the following general formula (1-1) or general formula (1-2). Mention may be made of azo compounds and pigments.

  Hereinafter, the azo compound and pigment represented by the general formula (1-1) or the general formula (1-2), tautomers thereof, salts or hydrates thereof will be described in detail.

(In General Formula (1-1) and General Formula (1-2), R _{1 to} R ₄ and n are the same as those defined in General Formula (1). X represents a carbon atom or a nitrogen atom, Ax represents a as defined in the general formula (1) together with the carbon atom and X, Bx of the substituent of the .R ₅ is .R ₅ representing the a as defined in the general formula (1) together with the carbon atom to represent a substituted group As for the substituent of R _5, an aliphatic oxy group, an aryloxy group, a thio group or a substituent is preferably used as long as it is a group that can be substituted with the groups described in the above-mentioned substituent group. (It is an amino group that may have, and more preferably an aliphatic oxy group or an amino group that may have a substituent.)

Many tautomers can be considered in the azo compounds and pigments represented by the general formulas (1), (1-1), and (1-2).
In the present invention, the azo compound and pigment represented by the general formula (1) preferably have a substituent that forms an intramolecular hydrogen bond or an intramolecular cross-hydrogen bond. It is more preferable to have at least one substituent that forms an intramolecular hydrogen bond, and it is particularly preferable to have at least one substituent that forms an intramolecular cross-hydrogen bond.

Factors preferable for this structure as a pigment include a nitrogen atom constituting a heterocyclic group contained in the azo pigment structure as shown by the general formula (1-1) or (1-2), and a hydrogen atom of the hydroxy group of the phenol ring. And oxygen atom, and azo group or its tautomer hydrazone group nitrogen atom, or carbonyl group substituted for azo component contained in azo pigment structure, phenol ring hydroxy group hydrogen atom and oxygen atom, and azo The nitrogen atom of the hydrazone group which is a group or a tautomer thereof easily forms a cross-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 (1-1) or the general formula (1-2) is increased ( It is more preferable because it is easy to form a higher order structure) and the required performance as a pigment is greatly improved in light fastness, heat stability, wet heat stability, water resistance, gas resistance and / or solvent resistance. An example.

  Specific examples of the azo compound and the azo pigment represented by the general formula (1), the general formula (1-1), and the general formula (1-2) are shown below, but the azo compound and the azo pigment of the present invention are shown below. Is 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 may be tautomeric structures other than those described. Needless to say.

  The pigment represented by the general formula (1), general formula (1-1), and general formula (1-2) of the present invention has a chemical structural formula of the general formula (1), (1-1), or the general formula ( 1-2) or a tautomer thereof may be used, and any crystal form pigment also called polymorph may be used.

  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 a crystal polymorph exists in the pigment represented by the general formula (1), general formula (1-1), and general formula (1-2) of the present invention, any polymorph may be used, and two kinds of polymorphs may be used. Although the mixture of the above polymorphs may be sufficient, it is preferable to have a single crystal form as a main component. That is, it is preferable that the crystalline polymorph 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 (SEM), IR (KBr method), etc. I can confirm.

  The tautomerism and / or crystal polymorphism described above can be controlled by the production conditions during the coupling reaction.

  In the present invention, the azo pigment represented by the general formula (1), the general formula (1-1), and the general formula (1-2) may be a hydrate containing water molecules in the crystal.

  Next, an example of a method for producing the azo pigment represented by the general formula (1) will be described. For example, a heterocyclic amine represented by the following general formula (4) is diazonium with non-aqueous acidity, a coupling reaction is performed with a compound represented by the following general formula (5) in an acidic state, and post-treatment by a conventional method is performed. It can carry out and can manufacture the azo pigment represented by General formula (6) of this invention. The azo pigment represented by the general formula (1) can be produced by performing the same operation using a heterocyclic amine corresponding to A of the general formula (1) instead of the general formula (4).

(In the formula, R ₅₅ , R ₅₆ and R ₅₈ are synonymous with those defined in the general formula (2).)

_(Wherein, R 1 to R ₄ have the same meanings as those defined by the general formula (1).)
The reaction scheme is shown below.

(In the formula, R _{1 to} R ₄ , R ₅₅ , R ₅₆ , R ₅₈ , and n have the same meanings as defined in general formula (1).)

Although the heterocyclic amine represented by the general formula (4) and the heterocyclic amine corresponding to the amino form of (A-1) to (A-30) may be available as commercial products, Specifically, it can be produced by a known and commonly used method, for example, the method described in Japanese Patent No. 4022271. The coupler represented by the general formula (5) can be obtained as a commercial product, but can be produced by the method described in JP-A-2008-13472 and a method analogous thereto. The diazoniumation reaction of the heterocyclic amine represented by the above reaction scheme is carried out at a temperature of 15 ° C. or less with a reagent such as sodium nitrite, nitrosylsulfuric acid, isoamyl nitrite in an acidic solvent such as sulfuric acid, phosphoric acid, and acetic acid. The reaction can be carried out for about 6 minutes to 6 minutes. The coupling reaction is carried out by reacting the diazonium salt obtained by the above-described method with the compound represented by the general formula (5) at 40 ° C. or less, preferably 25 ° C. or less for about 10 minutes to 12 hours. Can do.
The synthesis method in the case where n in the general formula (1), the general formula (1-1), and the general formula (1-2) is 2 or more is R _{1 to} R _{3 in the} general formula (4) or the general formula (5). , R ₅₅ , R ₅₆ , R ₅₈ and the like can be synthesized in the same manner as in the above scheme by synthesizing raw materials into which substitutable divalent, trivalent or tetravalent substituents are introduced.
In some cases, crystals are precipitated in this way, but in general, water or an alcohol solvent is added to the reaction solution to precipitate the crystals, and the crystals can be collected by filtration. it can. In addition, an alcohol solvent, water or the like can be added to the reaction solution to precipitate crystals, and the precipitated crystals can be collected by filtration. The crystals collected by filtration can be washed and dried as necessary to obtain an azo pigment represented by the general formula (1).

  Although the compound represented by the general formula (1), the general formula (1-1) and the general formula (1-2) is obtained as a crude azo pigment (crude) by the above production method, When used, it is desirable to perform post-processing. 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 formula (1), general formula (1-1) and general formula (1-2) of the present invention are preferably subjected to solvent heating treatment and / or solvent salt milling as 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 the inorganic salt, a water-soluble inorganic salt can be preferably used. For example, an inorganic salt such as sodium chloride, potassium chloride, sodium sulfate is preferably used. 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 a kneader, for example, a kneader or a mix muller can be used.

[Pigment dispersion]
The pigment dispersion of the present invention contains at least one azo pigment, tautomer, salt or hydrate represented by general formula (1), general formula (1-1), and general formula (1-2). Including seeds. 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 Polyhydric 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.

  When the aqueous pigment dispersion in the present invention contains an aqueous resin, the content is not particularly limited. For example, it can be 0 to 100% by mass with respect to the pigment.

  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.

  When the aqueous pigment dispersion in the present invention contains a surfactant, the content is not particularly limited. For example, it can be 0 to 100% by mass with respect to the pigment.

  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 fatty acid Examples include esters, polyoxyethylene fatty acid esters, polyoxyethylene alkylamines, fluorine-based materials, and silicon-based materials.

  The non-aqueous pigment dispersion of the present invention is obtained by dispersing the pigments represented by the general formula (1), general formula (1-1), and general formula (1-2) 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 contained in the pigment dispersion 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 pigment. 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 putting 3 ml of the pigment dispersion in a measuring cell. As parameters to be input at the time of measurement, ink viscosity was used as the viscosity, and pigment density was used as the density of the dispersed particles.

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

  The dispersion containing the azo compound of the present invention can also contain the above-mentioned components constituting the pigment dispersion, and the preferred concentration of the azo compound contained in the dispersion is the same as that described for the pigment dispersion. is there.

  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 compounds and azo pigments of the present invention include image recording materials for forming images, particularly color images, and specifically, thermal recording, including inkjet recording materials described in detail below. Materials, pressure-sensitive recording materials, recording materials using electrophotography, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc., preferably ink-jet recording materials, heat-sensitive recording materials, recording materials using electrophotography More preferably, it is an ink jet recording material.

  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 azo compound and the azo pigment of the present invention are used by adjusting physical properties such as solvent resistance, dispersibility, and heat mobility suitable for the application with a substituent. In addition, the azo compound and azo 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 compound of the present invention and an azo pigment. 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 for inkjet recording]
Next, the ink for inkjet recording of the present invention will be described.
The above-described dispersion 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 of the dispersion in the ink of the present invention is preferably in the range of 1 to 100% by mass, 3 to 20% in consideration of the hue, color density, saturation, transparency and the like of the image formed on the recording medium. % Is particularly preferable, and a range of 3 to 10% by mass is most preferable.

  It is preferable to contain 0.1 to 20 parts by mass of the azo compound or azo pigment of the present invention in 100 parts by mass of the ink of the present invention, and more preferably 0.2 to 10 parts by mass. The content is preferably 1 to 10 parts by mass. Further, in the ink of the present invention, other pigments may be used in combination with the 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 magenta pigments that can be applied 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 derivative 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, diglycerin. And ethylene oxide adducts.

  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.

  EXAMPLES The present invention will be specifically described below based on examples, but the present invention is not limited to these examples. Hereinafter, “parts” means parts by mass.

[Synthesis Example 1]
Synthesis of Specific Compound Example D-51 Specific Compound Example D-51 was synthesized by the following route.

Synthesis of Compound D-51 1.0 g of Compound (1) was dissolved in 10 ml of phosphoric acid. This solution was ice-cooled and kept at -5 to 0 ° C, 0.38 g of sodium nitrite was added and stirred for 1 hour to obtain a diazonium salt solution. Separately, the above diazonium salt solution was added at 10 ° C. or lower while stirring a solution obtained by adding 25 ml of methanol to 0.91 g of compound (0). Upon completion of the addition, the ice bath was removed and the mixture was further stirred for 2 hours. 25 ml of methanol was added to the reaction solution, and the mixture was stirred for 30 minutes. The precipitated crystals were separated by filtration and washed with 30 ml of cold methanol. The crystals were added to 50 ml of cold water in which 0.1 g of sodium bicarbonate was dissolved without drying, and stirred at 15 to 20 ° C. for 30 minutes. The precipitated crystals were separated by filtration, and further thoroughly washed with cold water. The obtained crystals were added to 40 ml of methanol and 20 ml of water without drying, and stirred at 60 ° C. for 60 minutes. Thereafter, the mixture was stirred at room temperature for 30 minutes, and the precipitated crystals were filtered and washed with cold methanol / water = 2/1. The obtained crystals were dried to obtain 1.2 g of the compound D-51 of the present invention. Yield 61%.
FIG. 1 shows an infrared absorption chart.

[Synthesis Example 2] Synthesis of Specific Compound Example D-52 Specific Compound Example D-52 was synthesized by the following route.

Synthesis of Compound (3) To 4.0 g of compound (2) and 5.9 g of dicyclohexylcarbodiimide, 2.7 g of aniline was added 5 ml of dimethylacetamide, and the mixture was stirred at 40 ° C. for 1 hour. The reaction solution was brought to 25 ° C., 50 ml of ethyl acetate and 50 ml of water were added, and the mixture was stirred for 10 minutes. The precipitated crystals were separated by filtration, the filtrate was separated, and the ethyl acetate layer was washed with 50 ml of water and dried over magnesium sulfate. Ethyl acetate was distilled off under reduced pressure to obtain 5.5 g of a compound (3) containing some dicyclohexylurea. Yield 92%.

Synthesis of Compound D-52 1.0 g of Compound (1) was dissolved in 10 ml of phosphoric acid. This solution was ice-cooled and kept at -5 to 0 ° C, 0.38 g of sodium nitrite was added and stirred for 1 hour to obtain a diazonium salt solution. Separately, the above-mentioned diazonium salt solution was added at 10 ° C. or lower while stirring a solution obtained by adding 25 ml of methoxyethanol to 1.3 g of compound (3). Upon completion of the addition, the ice bath was removed and the mixture was further stirred for 2 hours. 50 ml of methanol was added to the reaction solution and stirred for 30 minutes. The precipitated crystals were separated by filtration and washed with 30 ml of 40 ° C. methanol. The crystals were added to 50 ml of cold water in which 0.2 g of sodium bicarbonate was dissolved without drying, and stirred at 25 ° C. for 60 minutes. The precipitated crystals were separated by filtration, and further thoroughly washed with cold water. The obtained crystals were added to 40 ml of dimethylacetamide (DMAc) and 40 ml of water without drying, and stirred at 70 ° C. for 60 minutes. Thereafter, the mixture was stirred at room temperature for 30 minutes, and the precipitated crystals were filtered, washed with DMAc / water = 1/1, and further washed with sufficient water. The obtained crystals were dried to obtain 1.0 g of the compound D-52 of the present invention. Yield 45%.
FIG. 2 shows an infrared absorption chart.

Synthesis Example 3 Synthesis of Specific Compound Example D-53 Specific Compound Example D-53 was synthesized by the following route.

Synthesis of Compound (5) To 3.5 g of Compound (4) and 5.2 g of dicyclohexylcarbodiimide, 2.4 g of aniline was added 5 ml of dimethylacetamide, and the mixture was stirred at 40 ° C. for 1 hour. The reaction solution was brought to 25 ° C., 50 ml of ethyl acetate and 50 ml of water were added, and the mixture was stirred for 10 minutes. The precipitated crystals were separated by filtration, the filtrate was separated, and the ethyl acetate layer was washed with 50 ml of water and dried over magnesium sulfate. Ethyl acetate was distilled off under reduced pressure to obtain an oily substance. This was purified by silica gel column chromatography and developing solvent n-hexane / ethyl acetate = 10/1 to 5/1 to obtain 4.0 g of compound (5). Yield 76%.

Synthesis of Compound D-53 1.0 g of Compound (1) was dissolved in 10 ml of phosphoric acid. This solution was ice-cooled and kept at −5 to 0 ° C., 0.38 g of sodium nitrite was added and stirred for 1 hour to obtain a diazonium salt solution. Separately, the above diazonium salt solution was added at 10 ° C. or lower while stirring a solution obtained by adding 25 ml of methoxyethanol to 1.2 g of compound (5). Upon completion of the addition, the ice bath was removed and the mixture was further stirred for 2 hours. 80 ml of water was added to the reaction solution, and the mixture was stirred for 30 minutes. The precipitated crystals were separated by filtration and washed with sufficient water. The crystals were dissolved in 100 ml of methanol and 1.4 ml of triethylamine at room temperature, and filtered to remove insoluble matters. Methanol was concentrated to 50 ml, and 2 ml of acetic acid was added with stirring. The precipitated crystals were filtered and washed with 20 ml of cold methanol. The obtained crystals were added to 30 ml of methanol and 30 ml of water without drying, and stirred at 60 ° C. for 60 minutes. Thereafter, the mixture was stirred at room temperature for 30 minutes, and the precipitated crystals were filtered, washed with methanol / water = 1/1, and further washed with sufficient water. The obtained crystals were dried to obtain 1.2 g of the compound D-53 of the present invention. Yield 54%.
FIG. 3 shows an infrared absorption chart.

[Synthesis Example 4]
Synthesis of Specific Compound Example D-54 Specific Compound Example D-54 was synthesized by the following route.

Synthesis of Compound D-54 1.0 g of Compound (6) was dissolved in 10 ml of phosphoric acid. This solution was ice-cooled and kept at −5 to 0 ° C., 0.38 g of sodium nitrite was added and stirred for 1 hour to obtain a diazonium salt solution. Separately, the above diazonium salt solution was added at 10 ° C. or lower while stirring a solution obtained by adding 25 ml of methanol to 1.28 g of compound (7). Upon completion of the addition, the ice bath was removed and the mixture was further stirred for 2 hours. 25 ml of methanol was added to the reaction solution, and the mixture was stirred for 30 minutes. The precipitated crystals were separated by filtration and washed with 30 ml of cold methanol. The crystals were added to 50 ml of cold water in which 0.1 g of sodium bicarbonate was dissolved without drying, and stirred at 15 to 20 ° C. for 30 minutes. The precipitated crystals were separated by filtration, and further thoroughly washed with cold water. The obtained crystals were added to 40 ml of methanol and 20 ml of water without drying, and stirred at 60 ° C. for 60 minutes. Thereafter, the mixture was stirred at room temperature for 30 minutes, and the precipitated crystals were filtered and washed with cold methanol / water = 2/1. The obtained crystals were dried to obtain 1.3 g of the compound D-54 of the present invention. Yield 63%.

[Synthesis Example 5]
Synthesis of Specific Compound Example D-55 Specific compound example D-55 was synthesized by the following route.

Synthesis of Compound D-55 1.2 g of Compound (8) was dissolved in 10 ml of phosphoric acid. This solution was ice-cooled and kept at −5 to 0 ° C., 0.38 g of sodium nitrite was added and stirred for 1 hour to obtain a diazonium salt solution. Separately, the above diazonium salt solution was added at 10 ° C. or lower while stirring a solution obtained by adding 25 ml of methanol to 1.28 g of compound (7). Upon completion of the addition, the ice bath was removed and the mixture was further stirred for 2 hours. 25 ml of methanol was added to the reaction solution, and the mixture was stirred for 30 minutes. The precipitated crystals were separated by filtration and washed with 30 ml of cold methanol. The crystals were added to 50 ml of cold water in which 0.1 g of sodium bicarbonate was dissolved without drying, and stirred at 15 to 20 ° C. for 30 minutes. The precipitated crystals were separated by filtration, and further thoroughly washed with cold water. The obtained crystals were added to 40 ml of methanol and 20 ml of water without drying, and stirred at 60 ° C. for 60 minutes. Thereafter, the mixture was stirred at room temperature for 30 minutes, and the precipitated crystals were filtered and washed with cold methanol / water = 2/1. The obtained crystals were dried to obtain 1.6 g of the compound D-55 of the present invention. Yield 60%.

[Synthesis Example 1 of Comparative Compound]
Synthesis of Comparative Compound 1 Comparative compound 1 was synthesized by the following route.

  Water (15 ml) and concentrated hydrochloric acid (2.2 ml) were added to 2.1 g of the compound (a), and the mixture was stirred at -2 ° C to 2 ° C. To this solution, a solution obtained by dissolving 0.72 g of sodium nitrite in 5 ml of water was added dropwise over 10 minutes to obtain a diazonium salt solution. Separately, 10 ml of DMAc was added to 2.40 g of compound (b), and the above diazonium salt solution was added at 5 ° C. to 10 ° C. with stirring. Upon completion of the addition, the ice bath was removed and the mixture was further stirred for 2 hours. The precipitated crystals were separated by filtration and washed with 50 ml of water. The obtained crystal was recrystallized with 50 ml of methanol, cooled to 25 ° C., and the precipitated crystal was separated by filtration. The obtained crystal was dried to obtain 1.1 g of Comparative Compound 1. Yield 24%.

[Synthesis Example 2 of Comparative Compound]
Synthesis of Comparative Compound 2 Comparative compound 2 was synthesized by the following route.

  Comparative compound 2 was synthesized in the same manner as comparative compound 1. Yield 48%.

[Synthesis Example 3 of Comparative Compound]
Synthesis of Comparative Compound 3 Comparative compound 3 was synthesized by the following route.

  To 1.9 g of compound (d), 15 ml of water and 2.2 ml of concentrated hydrochloric acid were added, and the mixture was stirred at -2 ° C to 2 ° C. To this solution, a solution obtained by dissolving 0.72 g of sodium nitrite in 5 ml of water was added dropwise over 10 minutes to obtain a diazonium salt solution. Separately, 40 g of water and 2 g of sodium carbonate were added to 2.6 g of compound (b), and the above diazonium salt solution was added at 5 ° C. to 10 ° C. with stirring. Upon completion of the addition, the ice bath was removed and the mixture was further stirred for 2 hours. The reaction solution was added to 200 ml of saturated saline. The precipitated crystals were separated by filtration, washed with 30 ml of saturated brine and dried. The obtained crystals were heated with 100 ml of methanol, and insoluble matters were filtered. The solution was purified by Sephadex column chromatography, the water / methanol solution was concentrated, the precipitated crystals were filtered off, washed with methanol, and 1.7 g of Comparative Compound 3 was obtained. Yield 35%.

[Example 1]
Specific compound example D-51 pigment 2.5 parts, sodium oleate 0.5 parts, glycerin 5 parts and water 42 parts are mixed, and each 100 parts of zirconia beads having a diameter of 0.1 mm are mixed using a planetary ball mill. Dispersion was performed at 300 rpm for 6 hours. After the completion of dispersion, zirconia beads were separated to obtain pigment dispersion 1.

[Example 2]
A red pigment dispersion 2 was obtained in the same manner as in Example 1 except that Compound D-52 was used instead of Compound D-51 used in Example 1.

Example 3
A red pigment dispersion 3 was obtained in the same manner as in Example 1 except that Compound D-53 was used instead of Compound D-51 used in Example 1.

Example 4
A red pigment dispersion 4 was obtained in the same manner as in Example 1 except that Compound D-54 was used instead of Compound D-51 used in Example 1.

Example 5
A red pigment dispersion 5 was obtained in the same manner as in Example 1 except that Compound D-55 was used instead of Compound D-51 used in Example 1.

[Comparative Example 1]
A red comparative pigment dispersion 1 was obtained in the same manner as in Example 1 except that Comparative Compound 1 was used instead of Compound D-51 used in Example 1.

[Comparative Example 2]
A yellow comparative pigment dispersion 2 was obtained in the same manner as in Example 1 except that Comparative Compound 2 was used instead of Compound D-51 used in Example 1.

[Comparative Example 3]
A yellow comparative pigment dispersion 3 was obtained in the same manner as in Example 1, except that Comparative Compound 3 was used instead of Compound D-51 used in Example 1.

(Evaluation)
<Dispersion stability>
The volume average particle size of each pigment dispersion obtained above was measured by a conventional method using a dynamic light scattering particle size measuring device (Nikkiso Microtrack UPA150). The volume average particle diameter measured 2 hours after preparing the pigment dispersion and the volume average particle diameter after storage at 70 ° C. for 2 days are both 230 nm or less (good), either of which is 230 nm or more X (defect). The results are shown in Table 1.
<Evaluation of coloring power>
Each pigment dispersion obtained above was designated as 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 “coloring power (OD: Optical Density)” was evaluated according to the following criteria. The case where the OD was 1.6 or more was rated as 、, the case where it was 1.4 or more and less than 1.6, the case where it was 1.2 or more and less than 1.4, Δ, and the case where it was less than 1.2, ×. The results are shown in Table 1.
<Light resistance evaluation>
The coated product having an image density of 1.0 used for evaluating the coloring power was irradiated with xenon light (170000 lux .; in the presence of a cut filter of 325 nm or less) for 14 days using a fade meter, and the image density before and after the xenon irradiation was measured as the reflection density. It was measured using a meter and evaluated as a dye residual ratio [(post-irradiation density / pre-irradiation density) × 100%]. The results are shown in Table 1.

Example 6
The polymer dispersant represented by Dispersant 10 described on page 22 of International Publication No. WO06 / 064193 was neutralized with an aqueous potassium hydroxide solution. 30 parts by mass of the synthetic azo pigment (D-51) and 95 parts by mass of ion-exchanged water are added to 75 parts by mass of the resulting aqueous dispersant solution (solid content concentration: 20%) and mixed with a disper stirring blade.・ Roughly disperse. 600 parts by mass of zirconia beads were added to the mixed and roughly dispersed liquid, and this was dispersed with a disperser (sand grinder mill) for 4 hours, and then separated into beads and a dispersion. While stirring the resulting mixture, 2 parts by mass of polyethylene glycol diglycidyl ether was slowly added at 25 ° C., and the mixture was stirred at 50 ° C. for 6 hours. Furthermore, impurities were removed using an ultrafiltration membrane having a fractional molecular number of 300K, and this was attached to a filter having a pore size of 5 μm (acetylcellulose membrane, outer diameter: 25 mm, manufactured by Fuji Film Co., Ltd.). By filtering with a syringe and removing coarse particles, a pigment dispersion 6 (particle size 80 nm: measured using Nanotrac 150 (UPA-EX150) manufactured by Nikkiso Co., Ltd.) was obtained.

[Comparative Example 4]
Comparative pigment dispersion 4 was obtained in the same manner as in Example 6 except that Comparative Compound 1 was used instead of Compound D-51 used in Example 6.

Example 7
5% by mass of the pigment dispersion 6 obtained in Example 6, 10% by mass of glycerin, 5% by mass of 2-pyrrolidone, 2% by mass of 1,2-hexanediol, 2% by mass of triethylene glycol monobutyl ether, Each component was added so that it might become 0.5 mass% of propylene glycol, and 75.5 mass% of ion-exchange water, and the obtained liquid mixture was filtered with a 1 μm pore size filter (acetylcellulose membrane, outer diameter: 25 mm, Fujifilm Corporation). The pigment ink liquid 7 of the present invention was obtained by filtering with a syringe having a capacity of 20 ml equipped with a) and removing coarse particles.

[Comparative Example 5]
A comparative pigment ink liquid 5 was obtained in the same manner as in Example 7 except that the comparative pigment dispersion 4 obtained in Comparative Example 4 was used instead of the pigment dispersion 6 obtained in Example 6.

  In Table 2, “Ejection stability”, “Light fastness”, “Heat fastness”, “Ozone fastness”, “Metal gloss”, and “Ink liquid stability” are the same for each ink. ) Installed in a yellow ink liquid cartridge of an inkjet printer PX-V630 manufactured by the company, PX-V630 pigment ink liquid was used for the other color inks, and the image receiving sheet was a photographic paper <gloss> manufactured by Seiko Epson Corporation. In addition, the photographic paper Krispia <High gloss> manufactured by Seiko Epson Co., Ltd. recommends a single-color image pattern and green, red, and gray image patterns in which the density changes in a staircase pattern, and the image quality and ink ejection properties. And image robustness were evaluated. Evaluations other than metallic luster were performed in a single color.

  The following evaluation was performed on the inkjet inks of Example 7 (pigment ink liquid 7) and Comparative Example 5 (comparative pigment ink liquid 5). The results are shown in Table 2.

(Evaluation experiment)
1) About discharge stability, after setting a cartridge in a printer and confirming the protrusion of the ink from all the nozzles, 20 sheets of A4 were output and evaluated according to the following criteria.
A: No printing disturbance from the start to the end of printing B: Output with a printing disturbance occurs C: Printing is disturbed from the start to the end of printing 2) Regarding image storability, the following evaluations were made using print samples. Went.
[1] Light fastness is measured by measuring X-Rite's Photographic Densitometer 310 (X-rite 310) immediately after printing with Xenite light (100,000 lux) for 14 days using an Atlas weather meter. After the irradiation, the image density Cf was measured again, and the image remaining rate Cf / Ci × 100 was obtained and evaluated.
The image afterimage rate is evaluated at three points of reflection density of 1, 1.5 and 2. A is the case where the image remaining rate is 80% or more at any density, and B is the case where 1 or 2 points is less than 80%. The case where the concentration was less than 80% at all concentrations was defined as C.
[2] For heat fastness, the density before and after storing the print sample for 7 days under the condition of 80 ° C. and 60% RH was measured with a reflection densitometer X-rite 310, and the image residual ratio was determined and evaluated. . The image afterimage rate is evaluated at three points of reflection density of 1, 1.5 and 2, and A is the case where the image remaining rate is 95% or more at any density, and B is the case where 1 or 2 points is less than 95%. , C was defined as less than 95% at all concentrations.
[3] With regard to ozone resistance (ozone fastness), the sample is left in a box where the ozone gas concentration is set to 5 ppm (25 ° C; 50%) for 14 days. It measured using Rite310 and evaluated as image residual ratio. The reflection density was measured at three points of 1, 1.5 and 2.0. The ozone gas concentration in the box was set using an ozone gas monitor (model: OZG-EM-01) manufactured by APPLICS. The evaluation was made in three stages, with A as the case where the image remaining ratio was 80% or higher at any density, and B when 1 or 2 points were less than 80%, and C when less than 70% at all densities.
3) Presence or absence of occurrence of metallic luster: The yellow, green and red solid print portions were visually observed and evaluated with reflected light.
The case where the metallic luster was not visible was evaluated as “◯”, and the case where the metallic luster was visible was evaluated as “x”.
4) Ink liquid stability: After aging the pigment ink liquids of Examples and Comparative Examples at 60 ° C. for 10 days, the evaluation was made with “◯” indicating no change in the particle diameter in the pigment ink liquid and “X” indicating that there was a change in the particle diameter. did. The results are shown in Table 2 below.

From the results in Table 2, it was found that the pigment ink liquid using the pigment of the present invention was excellent in ejection property and fastness, suppressed the occurrence of metallic luster, and excellent in pigment ink liquid stability.
As is apparent from the results in Table 2, it can be seen that the system using the ink liquid of the present invention is excellent in all performance. In particular, the light fastness, ozone fastness and ink liquid stability are superior to the comparative examples.

Example 9
An image of the pigment ink liquid prepared in Example 7 was printed on Fujifilm's inkjet paper photo glossy paper “Painting” with PX-V630 manufactured by Epson Corporation. When similar evaluations were made, similar results were obtained.
As is clear from the results of Tables 1 and 2, Pigment Dispersions 1 to 5 and 6 and the pigment ink liquid 7 using the pigment of the present invention are excellent in color tone and exhibit high coloring power and light resistance.
Therefore, the pigment dispersion using the pigment of the present invention can be suitably used, for example, for printing ink such as inkjet.

Claims (8)

An azo compound represented by the following general formula (1), a tautomer thereof, a salt or a hydrate thereof.

(In the general formula (1), R _{1 to} R ₃ are each independently a hydrogen atom, a hydroxyl group, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carboxyl group, a carbamoyl group, or an acylamino group. , a sulfonamido group, a carbamoylamino group, a sulfamoyl group, an aliphatic oxy group, an aliphatic thio group, a cyano group or a halogen atom, but they do not form an aromatic ring bonded to each other .R ₄ is an amino group, fat Represents a heterocyclic group bonded with a group oxy group or a nitrogen atom, A represents an aromatic 5- to 6-membered heterocyclic group, n represents an integer of 1 to 4, and when n = 2, R _{1 to} R Represents a dimer via ₃ or A. When n = 3, it represents a trimer via R _{1 to} R ₃ or A. When n = 4, it represents a R _{1 to} R ₃ or A. Represents a tetramer, provided that the general formula (1 The azo compound represented by) does not include a metal chelate dye form.) In the azo compound represented by the general formula (1), A is represented by any one of the following general formulas (A-1) to (A-30). Compound, its tautomer, salt or hydrate thereof.

(In the general formulas (A-1) to (A-30), R _{51 to} R ₅₈ each independently represents a hydrogen atom or a substituent, and adjacent substituents are bonded to each other to form a 5- to 6-membered ring. R ₅₉ represents a substituent, and adjacent substituents may be bonded to each other to form a 5- to 6-membered ring, and R ₆₀ and R ₆₁ are each independently a hydrogen atom. Or represents a substituent, * represents a bonding position with the azo group of the general formula (1). An azo pigment represented by the following general formula (1), a tautomer thereof, a salt or a hydrate thereof.

(In the general formula (1), R _{1 to} R ₃ are each independently a hydrogen atom, a hydroxyl group, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carboxyl group, a carbamoyl group, or an acylamino group. , a sulfonamido group, a carbamoylamino group, a sulfamoyl group, an aliphatic oxy group, an aliphatic thio group, a cyano group or a halogen atom, but they do not form an aromatic ring bonded to each other .R ₄ is an amino group, fat Represents a heterocyclic group bonded with a group oxy group or a nitrogen atom, A represents an aromatic 5- to 6-membered heterocyclic group, n represents an integer of 1 to 4, and when n = 2, R _{1 to} R Represents a dimer via ₃ or A. When n = 3, it represents a trimer via R _{1 to} R ₃ or A. When n = 4, it represents a R _{1 to} R ₃ or A. Represents a tetramer, provided that the general formula (1 The azo pigment represented by) does not include the form of a metal chelate dye.) The azo pigment according to claim 3, wherein in the azo pigment represented by the general formula (1), A is represented by any one of the general formulas (A-1) to (A-30). , Tautomers thereof, salts or hydrates thereof.

(In the general formulas (A-1) to (A-30), R _{51 to} R ₅₈ each independently represents a hydrogen atom or a substituent, and adjacent substituents are bonded to each other to form a 5- to 6-membered ring. R ₅₉ represents a substituent, and adjacent substituents may be bonded to each other to form a 5- to 6-membered ring, and R ₆₀ and R ₆₁ are each independently a hydrogen atom. Or represents a substituent, * represents a bonding position with the azo group of the general formula (1). The azo pigment represented by the general formula (1) is represented by the following general formula (2), the azo pigment according to claim 4, a tautomer thereof, a salt thereof, or a hydration thereof object.

(In General Formula (2), R _{21 to} R ₂₃ are each independently a hydrogen atom, a hydroxyl group, an aliphatic group, an aryl group, a heterocyclic group, an aliphatic oxycarbonyl group, a carboxyl group, a carbamoyl group, or an acylamino group. , a sulfonamido group, a carbamoylamino group, a sulfamoyl group, an aliphatic oxy group, an aliphatic thio group, a cyano group or a halogen atom, bonded to each other .R ₂₄ but they do not form an aromatic ring is a hydrogen atom, the total An alkyl group having 1 to 8 carbon atoms, an aryl group having 6 to 10 carbon atoms, a heterocyclic group having 2 to 12 carbon atoms in total, which may be saturated or unsaturated, A ₂ Is represented by any of the above general formulas (A-10) to (A-30), n represents an integer of 1 to 4. When n = 2, R _{21 to} R ₂₃ or A ₂ is represented by Represents a dimer via For n = 3 in the case of .n = 4 representing a trimer formed through _R 21 _{to R 23} or _{A 2} represents a tetramer formed through _R 21 _{to R 23} or _{A 2.)}   A dispersion comprising at least one azo compound according to claim 1 or claim 2 or an azo pigment according to any one of claims 3 to 5.   A coloring composition comprising at least one azo compound according to claim 1 or claim 2 or an azo pigment according to any one of claims 3 to 5.   An ink for inkjet recording, comprising the dispersion according to claim 7.

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