JP2009242488A - Azo pigment, method for producing the same, pigment dispersion including the same, coloring composition and ink-jet recording ink - Google Patents

Abstract

（一般式（１）中、Ｘ₁、Ｘ₂はそれぞれ独立にハメットのσｐ値が０．２以上の電子求引性基を表す。Ｙ₁、Ｙ₂、Ｒ₁、Ｒ₂、Ｇ₁、Ｇ₂、Ｐ₁、Ｐ₂、Ｑ₁、Ｑ₂はそれぞれ独立に水素原子または置換基を表す。Ｇは５〜６員ヘテロ環を構成することができる非金属原子団を表す。Ｗは、Ｇが構成するヘテロ環に結合可能な置換基を表す。ｔは０〜４の整数を表す。）
【選択図】 なしAn azo pigment and a pigment dispersion, a colored composition, an ink for ink jet recording, and an azo compound, which are excellent in color characteristics such as coloring power and hue and excellent in durability such as light resistance.
An azo pigment represented by the following general formula (1), a salt thereof, a hydrate, and a tautomer thereof.
General formula (1):

(In the general formula (1), X ₁ and X ₂ each independently represents an electron withdrawing group having a Hammett's σp value of 0.2 or more. Y ₁ , Y ₂ , R ₁ , R ₂ , G ₁ , G ₂ , P ₁ , P ₂ , Q ₁ and Q ₂ each independently represents a hydrogen atom or a substituent, G represents a nonmetallic atomic group capable of constituting a 5- to 6-membered heterocycle, W is And represents a substituent that can be bonded to the heterocycle formed by G. t represents an integer of 0 to 4.)
[Selection figure] None

Description

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

The dyes and pigments used in each of the above applications must have the following properties in common. That is, it has preferable absorption characteristics in terms of color reproducibility, fastness under environmental conditions to be used, for example, light resistance, heat resistance, good resistance to oxidizing gases such as ozone, and the like. In addition, when the pigment is a pigment, it is substantially insoluble in water and organic solvents and has good chemical fastness, and even when used as particles, the preferred absorption characteristics in the molecular dispersion state are impaired. It is also necessary to have properties such as absence. The required characteristics can be controlled by the strength of intermolecular interaction, but it is difficult to achieve both because they are in a trade-off relationship.
In addition, when a dye is used as a pigment, it has a particle size and a particle shape necessary for expressing desired transparency or concealment, fastness under environmental conditions used, for example, Light resistance, heat resistance, resistance to oxidizing gases such as ozone, chemical fastness to other organic solvents and sulfurous acid gas, etc., and dispersion to fine particles in the medium used Properties such as a stable state are also required. Since these properties are greatly influenced not only by the chemical structure but also by the particle size, particle shape, and crystallinity, these controls are very important (see, for example, Patent Document 1). In particular, there is a strong demand for pigments that have a good yellow hue, have high coloring power among light, wet heat, and active gases in the environment, and are fast to light.

  In other words, the required performance for pigments is more diverse than dyes that require performance as pigment molecules, and not only the performance as pigment molecules, but also the above requirements as solids (fine particle dispersions) as aggregates of pigment molecules All performance needs to be satisfied. As a result, the group of compounds that can be used as pigments is extremely limited compared to dyes, and even if high-performance dyes are derived into pigments, there are only a few that can satisfy the required performance as fine particle dispersions. It cannot be developed. This is confirmed by the fact that the number of pigments registered in the color index is less than 1/10 of the number of dyes.

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

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

  Patent Document 5 discloses a dye having an absorption characteristic excellent in color reproducibility and sufficient fastness. However, since all of the specific compounds described in the patent document are dissolved in water or an organic solvent, the chemical fastness is not sufficient.

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

JP 2004-26930 A JP-A-56-38354 U.S. Pat. No. 2,936,306 Japanese Patent Laid-Open No. 11-1000051 JP 2003-277661 A

  The present invention provides an azo pigment having excellent color characteristics such as coloring power and hue, and excellent durability such as light resistance, a pigment dispersion containing the pigment, a coloring composition, and an inkjet recording ink. Objective.

  As a result of intensive studies in view of the above circumstances, the present inventors have obtained a novel azo pigment, which has been found to have excellent color characteristics and durability, and completed the present invention.

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

(In the general formula (1), X ₁ and X ₂ each independently represents an electron withdrawing group having a Hammett's σp value of 0.2 or more. Y ₁ , Y ₂ , R ₁ , R ₂ , G ₁ , G ₂ , P ₁ , P ₂ , Q ₁ and Q ₂ each independently represents a hydrogen atom or a substituent, G represents a nonmetallic atomic group capable of constituting a 5- to 6-membered heterocycle, W is And represents a substituent that can be bonded to the heterocycle formed by G. t represents an integer of 0 to 4.)
[2]
The azo pigment represented by the general formula (1) is an azo pigment represented by the following general formula (2), its azo pigment, its salt, hydrate, and their Tautomers of.
General formula (2)

(In the general formula (2), X ₁ and X ₂ each independently represent an electron withdrawing group having a Hammett's σp value of 0.2 or more. Y ₁ , Y ₂ , G ₁ , G ₂ , R ₁ , R ₂ each independently represents a hydrogen atom or a substituent, G represents a nonmetallic atomic group capable of constituting a 5- to 6-membered heterocycle, and W represents a substituent that can be bonded to the heterocycle constituting G. T represents an integer of 0 to 4.)
[3]
The azo pigment according to [1] or [2], wherein the azo pigment represented by the general formula (1) or (2) is an azo pigment represented by the following general formula (3): Its salts, hydrates and their tautomers.
General formula (3)

(In the general formula (3), X ₁ and X ₂ each independently represents an electron withdrawing group having a Hammett's σp value of 0.2 or more. Y ₁ , Y ₂ , G ₁ , G ₂ , R ₁ , R ₂ each independently represents a hydrogen atom or a substituent, G ′ represents a non-metallic atomic group capable of constituting a 6-membered nitrogen-containing heterocycle, and W can be bonded to the heterocycle constituting G ′. And t represents an integer of 0 to 4.)
[4]
[1] or [2], wherein the azo pigment represented by the general formula (1), (2) or (3) is an azo pigment represented by the following general formula (4): Azo pigments, salts, hydrates thereof and tautomers thereof.
General formula (4)

(In the general formula (4), X ₁ and X ₂ each independently represents an electron withdrawing group having a Hammett's σp value of 0.2 or more. Y ₁ , Y ₂ , R ₁ and R ₂ are each independently Represents a hydrogen atom or a substituent, G ′ represents a non-metallic atomic group capable of constituting a 6-membered nitrogen-containing heterocycle, and W represents a substituent capable of bonding to the heterocycle constituting G ′. t represents an integer of 0 to 4. X ₁₁ and X ₁₂ each independently represents a heteroatom, and G ₁₁ and G ₁₂ each independently represent a nonmetallic atomic group for forming a heterocycle.
[5]
In the azo pigment represented by the general formula (4), the nitrogen-containing heterocycle represented by G ₁₁ and G ₁₂ is at least one selected from (G-1) to (G-13) in the following general formula (5). The azo pigment according to any one of [1] to [4], a salt thereof, a hydrate, and a tautomer thereof, which is a seed.
General formula (5):

(* Represented by (G-1) to (G-13) in the general formula (5) represents a binding site with the N atom on the pyrazole ring represented by the general formula (4). Z _{11 to} Z ₁₄ each represent a group that can be bonded to a heterocycle. G ″ in (G-13) represents a nonmetallic atomic group that can form a heterocycle.)
[6]
A pigment dispersion comprising at least one of the azo pigments according to any one of [1] to [5], salts thereof, hydrates, and tautomers thereof.
[7]
A coloring composition comprising at least one of the azo pigments, salts, hydrates and tautomers thereof according to any one of [1] to [5].
[8]
An ink for inkjet recording, comprising at least one of the azo pigments, salts, hydrates, and tautomers thereof according to any one of [1] to [5].

  ADVANTAGE OF THE INVENTION According to this invention, the azo pigment which is excellent in color characteristics, such as coloring power and a hue, and is excellent also in durability, such as light resistance, is provided. By dispersing the pigment of the present invention in various media, a pigment dispersion, a colored composition, and an ink jet recording ink excellent in color characteristics, durability and dispersion stability can be obtained. The pigment dispersion can be used, for example, in printing inks such as inkjet, color toners for electrophotography, displays such as LCDs and PDPs, color filters used in image sensors such as CCDs, paints, and colored plastics. it can.

Hereinafter, the present invention will be described in detail.
Here, Hammett's substituent constant σp value used in the present specification will be described briefly.
Hammett's rule is a method for determining the effect of substituents on the reaction or equilibrium of benzene derivatives. P. A rule of thumb proposed by Hammett, which is widely accepted today. Substituent constants determined by Hammett's rule include a σp value and a σm value, and these values can be found in many general books. A. Dean, “Lange's Handbook of Chemistry”, 12th edition, 1979 (Mc Graw-Hill) and “Chemicals” special edition, 122, 96-103, 1979 (Nankodo). In the present invention, each substituent is limited or explained by Hammett's substituent constant σp, which means that it is limited only to a substituent having a known value that can be found in the above-mentioned book. However, it goes without saying that even if the value is unknown, it also includes a substituent that would be included in the range when measured based on Hammett's rule. The compounds represented by the general formulas (1) to (5) of the present invention are not benzene derivatives, but the σp value is used as a scale indicating the electronic effect of the substituent regardless of the substitution position. In the present invention, the σp value will be used in this sense.

[Azo pigment]
The azo pigment in the present invention is represented by the general formula (1).

Hereinafter, the azo pigment represented by the general formula (1), tautomers thereof, salts or hydrates thereof will be described in detail.
General formula (1):

（一般式（１）中、Ｘ₁、Ｘ₂はそれぞれ独立にハメットのσｐ値が０．２以上の電子求引性基を表す。Ｙ₁、Ｙ₂、Ｒ₁、Ｒ₂、Ｇ₁、Ｇ₂、Ｐ₁、Ｐ₂、Ｑ₁、Ｑ₂はそれぞれ独立に水素原子または置換基を表す。Ｇは５〜６員ヘテロ環を構成する事ができる非金属原子団を表す。Ｗは、Ｇが構成するヘテロ環に結合可能な置換基を表す。ｔは０〜４の整数を表す。）

(In the general formula (1), X ₁ and X ₂ each independently represents an electron withdrawing group having a Hammett's σp value of 0.2 or more. Y ₁ , Y ₂ , R ₁ , R ₂ , G ₁ , G ₂ , P ₁ , P ₂ , Q ₁ , and Q ₂ each independently represent a hydrogen atom or a substituent, G represents a non-metallic atomic group that can form a 5- to 6-membered heterocyclic ring, And represents a substituent that can be bonded to the heterocycle formed by G. t represents an integer of 0 to 4.)

  Hereinafter, the general formula (1) will be described in more detail.

In the general formula (1), Y ₁ , Y ₂ , R ₁ , R ₂ , G ₁ , G ₂ , P ₁ , P ₂ , Q ₁ and Q ₂ each independently represent a hydrogen atom or a substituent.
W represents a substituent that can be bonded to the heterocycle formed by G. When a plurality of W are present, they each independently represent a substituent.

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

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

In the general formula (1), X ₁ and X ₂ represent an electron withdrawing group having a Hammett's substituent constant σp value of 0.20 or more, and a σp value of 0.30 or more. It is preferable. The upper limit is 1.0 or less electron withdrawing group.

Specific examples of X ₁ and X ₂ which are electron withdrawing groups having a σp value of 0.20 or more include acyl group, acyloxy group, carbamoyl group, alkyloxycarbonyl group, aryloxycarbonyl group, cyano group, nitro group Dialkylphosphono group, diarylphosphono group, diarylphosphinyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, sulfonyloxy group, acylthio group, sulfamoyl group, thiocyanate group, thiocarbonyl group, A halogenated alkyl group, a halogenated alkoxy group, a halogenated aryloxy group, a halogenated alkylamino group, a halogenated alkylthio group, an aryl group substituted with another electron-withdrawing group having a σp value of 0.20 or more, hetero Ring group, halogen atom, azo group, or Noshianeto group, and the like.

Preferred examples of X ₁ and X ₂ are each independently an acyl group having 2 to 12 carbon atoms, an acyloxy group having 2 to 12 carbon atoms, a carbamoyl group having 1 to 12 carbon atoms, and an alkyloxycarbonyl having 2 to 12 carbon atoms. Group, aryloxycarbonyl group having 7 to 18 carbon atoms, cyano group, nitro group, alkylsulfinyl group having 1 to 12 carbon atoms, arylsulfinyl group having 6 to 18 carbon atoms, alkyl having 1 to 12 carbon atoms A sulfonyl group, an arylsulfonyl group having 6 to 18 carbon atoms, a sulfamoyl group having 0 to 12 carbon atoms, a halogenated alkyl group having 1 to 12 carbon atoms, a halogenated alkyloxy group having 1 to 12 carbon atoms, and 1 to 12 carbon atoms A halogenated alkylthio group, a C7-18 halogenated aryloxy group, a carbon number of 7 substituted with 2 or more other electron withdrawing groups of σp0.20 or more 18 aryl group, and a nitrogen atom, an oxygen atom or 5-8 membered ring having sulfur atom include a heterocyclic group having 1 to 18 carbon atoms.

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

In the general formula (1), preferable examples of G ₁ and G ₂ include a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted group. An alkynyl group, a substituted or unsubstituted aralkyl group, a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or an acyl group . Particularly preferred substituents are a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group, a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, or an acyl group. Preferred substituents are preferably substituted or unsubstituted aryl groups, substituted or unsubstituted heterocyclic groups, particularly preferably substituted or unsubstituted heterocyclic groups, and substituted or unsubstituted nitrogen-containing heterocyclic groups. Is most preferred. Examples of the substituent include the same substituents as those exemplified in Y ₁ , Y ₂ , R ₁ , R ₂ , G ₁ , G ₂ , P ₁ , P ₂ , and Q ₁ in the general formula (1). be able to.

In the general formula (2), preferred examples of Y ₁ and Y ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted total carbon number of C6 to C18. An aryl group, a substituted or unsubstituted heterocyclic group having a total carbon number of C4 to C12, a substituted or unsubstituted alkyloxy group having a total carbon number of C1 to C12, a substituted or unsubstituted alkylthio group having a total carbon number of C1 to C12, A substituted or unsubstituted aryloxy group having a total carbon number of C6 to C18 and a substituted or unsubstituted arylthio group having a total carbon number of C6 to C18 are preferable, and among them, a hydrogen atom and a linear alkyl having a total carbon number of C1 to C8 A group and / or a branched alkyl group are preferred, particularly a hydrogen atom or a C1-C8 alkyl group is preferred, and a hydrogen atom is most preferred.

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

When R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W represent a monovalent substituent, examples of the monovalent substituent are independently a halogen atom, an alkyl group, a cyclo Alkyl group, aralkyl group, alkenyl group, alkynyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, Alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (alkylamino group, arylamino group), acylamino group (amide group), aminocarbonylamino group (ureido group), alkoxycarbonylamino group, aryloxycarbonylamino group, Sulfamoylamino group, alkylsulfonylamino group, arylsulfuryl Nylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, phosphino group Phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, azo group, or imide group, each of which may further have a substituent.

  Among them, particularly preferred substituents W are each independently a halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, alkoxy group, amide group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl. Group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group or alkoxycarbonyl group, halogen atom, alkyl group, aryl group, cyano group, hydroxyl group, alkylsulfonyl group, arylsulfonyl group, heterocyclic group or alkoxycarbonyl group And an alkyl group, an aryl group, a hydroxyl group, and an alkoxycarbonyl group are most preferable.

Particularly preferred R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ and Q ₂ are each independently a hydrogen atom, halogen atom, alkyl group, aryl group, heterocyclic group, cyano group, hydroxyl group, alkoxy group, amide Group, ureido group, alkylsulfonylamino group, arylsulfonylamino group, sulfamoyl group, alkylsulfonyl group, arylsulfonyl group, carbamoyl group, or alkoxycarbonyl group, especially hydrogen atom, halogen atom, alkyl group, aryl group, cyano Group, hydroxyl group, alkylsulfonyl group, arylsulfonyl group, heterocyclic group or alkoxycarbonyl group are preferred, and hydrogen atom, alkyl group, aryl group, hydroxyl group and alkoxycarbonyl group are most preferred.

Hereinafter, R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W will be described in more detail.

The halogen atom represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W represents a chlorine atom, a bromine atom or an iodine atom. Of these, a chlorine atom or a bromine atom is preferable, and a chlorine atom is particularly preferable.

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

The cycloalkyl group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 5 to 30 carbon atoms. Examples of the substituent group include the same as _{R 1, R 2, P 1} , P 2, Q 1, substituents listed in represented by Q _2, and W in the general formula (1). Examples of the cycloalkyl group may include cyclohexyl, cyclopentyl, or 4-n-dodecylcyclohexyl.

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

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

The alkynyl group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is a substituted or unsubstituted alkynyl group having 2 to 30 carbon atoms such as ethynyl or propargyl. I can list them.

The aryl group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms such as phenyl, p-tolyl, naphthyl, m-chlorophenyl or o-hexadecanoylaminophenyl. Examples of the substituent group include the same as _{R 1, R 2, P 1} , P 2, Q 1, substituents listed in represented by Q _2, and W in the general formula (1).

The heterocyclic group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic compound. It is a monovalent group from which one hydrogen atom has been removed, and they may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms.
Examples of the substituent group include the same as _{R 1, R 2, P 1} , P 2, Q 1, substituents listed in represented by Q _2, and W in the general formula (1).
Examples of the heterocyclic group include, but are not limited to, substitution positions: pyridine, pyrazine, pyridazine, pyrimidine, triazine, quinoline, isoquinoline, quinazoline, cinnoline, phthalazine, quinoxaline, pyrrole, indole, furan, benzofuran, thiophene Benzothiophene, pyrazole, imidazole, benzimidazole, triazole, oxazole, benzoxazole, thiazole, benzothiazole, isothiazole, benzisothiazole, thiadiazole, isoxazole, benzisoxazole, pyrrolidine, piperidine, piperazine, imidazolidine, thiazoline, etc. Can be mentioned.

  Furthermore, a pyridine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring are preferable. Among them, a pyridine ring, a pyrimidine ring, and a triazine ring are preferable, and a 2-pyridine, 2,4-pyrimidine ring, and an s-triazine ring are most preferable.

The alkoxy group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W includes a substituted or unsubstituted alkoxy group. As the substituted or unsubstituted alkoxy group, an alkoxy group having 1 to 30 carbon atoms is preferable. Examples of the substituent group include the same as _{R 1, R 2, P 1} , P 2, Q 1, substituents listed in represented by Q _2, and W in the general formula (1). Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

The aryloxy group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. Examples of the substituent group include the same as _{R 1, R 2, P 1} , P 2, Q 1, substituents listed in represented by Q _2, and W in the general formula (1). Examples of the aryloxy group include phenoxy, 2-methylphenoxy, 4-t-butylphenoxy, 3-nitrophenoxy, 2-tetradecanoylaminophenoxy and the like.

The silyloxy group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a silyloxy group having 3 to 20 carbon atoms, such as trimethylsilyloxy, t-butyldimethylsilyloxy, etc. Can be mentioned.

The heterocyclic oxy group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. . Examples of the substituent group include the same as _{R 1, R 2, P 1} , P 2, Q 1, substituents listed in represented by Q _2, and W in the general formula (1). Examples of the heterocyclic oxy group include 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy and the like.

The acyloxy group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is a formyloxy group, a substituted or unsubstituted alkylcarbonyloxy group having 2 to 30 carbon atoms, 6 carbon atoms To 30 substituted or unsubstituted arylcarbonyloxy groups are preferable, and examples of the substituent are represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in the general formula (1). And the same substituents as mentioned above. Examples of the acyloxy group include formyloxy, acetyloxy, pivaloyloxy, stearoyloxy, benzoyloxy, p-methoxyphenylcarbonyloxy and the like.

The carbamoyloxy group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted carbamoyloxy group having 1 to 30 carbon atoms. Can be the same as the substituents exemplified in R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in the general formula (1). Examples of the carbamoyloxy group include, for example, N, N-dimethylcarbamoyloxy, N, N-diethylcarbamoyloxy, morpholinocarbonyloxy, N, N-di-n-octylaminocarbonyloxy, Nn-octylcarbamoyl. Examples include oxy.

The alkoxycarbonyloxy group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted alkoxycarbonyloxy group having 2 to 30 carbon atoms. As the above, the same substituents as those represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in the general formula (1) can be exemplified. Examples of the alkoxycarbonyloxy group include methoxycarbonyloxy, ethoxycarbonyloxy, t-butoxycarbonyloxy, n-octylcarbonyloxy and the like.

The aryloxycarbonyloxy group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. And examples of the substituent include the same substituents as those described above represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in the general formula (1). Can do. Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy and the like.

The amino group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, a substituted or unsubstituted alkylamino group having 6 to 30 carbon atoms, or An unsubstituted arylamino group is preferred, and examples of the substituent include the substituents represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in the general formula (1). The same thing can be mentioned. Examples of the amino group include, for example, amino, methylamino, dimethylamino, anilino, N-methyl-anilino, diphenylamino, hydroxyethylamino, carboxyethylamino, sulfoethylamino, 3,5-dicarboxyanilino And so on.

The acylamino group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, 6 carbon atoms. To 30 substituted or unsubstituted arylcarbonylamino groups are preferable, and examples of the substituent are represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in the general formula (1). And the same substituents as mentioned above. Examples of the acylamino group include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino, and the like.

The aminocarbonylamino group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. As examples, the same substituents as those represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in the general formula (1) can be mentioned. Examples of the aminocarbonylamino group include carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino and the like.

The alkoxycarbonylamino group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. As the above, the same substituents as those represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in the general formula (1) can be exemplified. Examples of the alkoxycarbonylamino group include methoxycarbonylamino, ethoxycarbonylamino, t-butoxycarbonylamino, n-octadecyloxycarbonylamino, N-methyl-methoxycarbonylamino and the like.

The aryloxycarbonylamino group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms. Examples of the group include the same substituents as mentioned in the general formula (1) represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino and the like.

The sulfamoylamino group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms. Examples of the group include the same substituents as mentioned in the general formula (1) represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W. Examples of the sulfamoylamino group include sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino and the like.

The alkyl and arylsulfonylamino groups represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W are substituted or unsubstituted alkylsulfonylamino groups having 1 to 30 carbon atoms, 6 carbon atoms To 30 substituted or unsubstituted arylsulfonylamino groups. Examples of the substituent are represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in the general formula (1). And the same substituents as mentioned above. Examples of the alkylsulfonylamino group and arylsulfonylamino group include, for example, methylsulfonylamino, butylsulfonylamino, phenylsulfonylamino, 2,3,5-trichlorophenylsulfonylamino, p-methylphenylsulfonylamino and the like. I can do it.

The alkylthio group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted alkylthio group having 1 to 30 carbon atoms. The same substituents as those represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in the general formula (1) can be exemplified. Examples of the alkylthio group include methylthio, ethylthio, n-hexadecylthio and the like.

The arylthio group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms. Examples thereof include the same substituents as those represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in Formula (1). Examples of the arylthio group include phenylthio, p-chlorophenylthio, m-methoxyphenylthio and the like.

The heterocyclic thio group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. As examples, the same substituents as those represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in the general formula (1) can be mentioned. Examples of the heterocyclic thio group include 2-benzothiazolylthio, 1-phenyltetrazol-5-ylthio and the like.

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

The alkyl and arylsulfinyl groups represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W are substituted or unsubstituted alkylsulfinyl groups having 1 to 30 carbon atoms and 6 to 30 substituents. Alternatively, an unsubstituted arylsulfinyl group is preferred, and examples of the substituent include the substituents represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in the general formula (1). The same thing as a group can be mentioned. Examples of the alkyl and arylsulfinyl groups include methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl and the like.

The alkyl and arylsulfonyl groups represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W are substituted or unsubstituted alkylsulfonyl groups having 1 to 30 carbon atoms and 6 to 30 substituents. Alternatively, an unsubstituted arylsulfonyl group is preferred, and examples of the substituent include the substituents represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in the general formula (1). The same thing as a group can be mentioned. Examples of the alkyl and arylsulfonyl groups include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl and the like.

The acyl group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, or a carbon number having 7 to 30 carbon atoms. Or a substituted or unsubstituted arylcarbonyl group, or a heterocyclic carbonyl group bonded to a carbonyl group with a substituted or unsubstituted carbon atom having 4 to 30 carbon atoms is preferred. Examples of the substituent include those represented by the general formula (1) Examples thereof include the same substituents as those represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W. Examples of the acyl group include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl and the like.

The aryloxycarbonyl group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms. Examples thereof include the same substituents as those described above represented by R1, R2, P1, P2, Q1, Q2 and W in the general formula (1). Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl, and the like.

The alkoxycarbonyl group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. In the general formula (1), those represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W can be exemplified. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and the like.

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

The phosphino group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms. The same substituents as those represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in the general formula (1) can be exemplified. Examples of the phosphino group include dimethylphosphino, diphenylphosphino, methylphenoxyphosphino and the like.

The phosphinyl group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms. The same substituents as those represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W in the general formula (1) can be exemplified. Examples of the phosphinyl group include phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl and the like.

The phosphinyloxy group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms. Examples of the group include the same substituents as mentioned in the general formula (1) represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W. Examples of the phosphinyloxy group include diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.

The phosphinylamino group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms. Examples of the group include the same substituents as mentioned in the general formula (1) represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W. Examples of the phosphinylamino group include dimethoxyphosphinylamino and dimethylaminophosphinylamino.

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

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

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

The heterocyclic thio group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W includes a heterocyclic thio group having a substituent and an unsubstituted heterocyclic thio group. The heterocyclic thio group preferably has a 5-membered or 6-membered heterocyclic ring. Examples of the substituent include an ionic hydrophilic group. Examples of the heterocyclic thio group include a 2-pyridylthio group.

The sulfinyl group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W includes an alkylsulfinyl group and an arylsulfinyl group. Examples of the sulfinyl group include a 3-sulfopropylsulfinyl group and a 3-carboxypropylsulfinyl group.

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

The acyl group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W includes an acyl group having a substituent and an unsubstituted acyl group. The acyl group is preferably an acyl group having 1 to 12 carbon atoms when a substituent is removed. Examples of the substituent include an ionic hydrophilic group. Examples of the acyl group include an acetyl group and a benzoyl group.

Examples of the ionic hydrophilic group represented by R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W include a sulfo group, a carboxyl group, a phosphono group and a quaternary ammonium group. As the ionic hydrophilic group, a carboxyl group and a sulfo group are preferable. The carboxyl group and the sulfo group may be in a salt state, and examples of the counter ion forming the salt include ammonium ion, alkali metal ion (eg, calcium ion, barium ion) and organic cation (eg, tetramethyl group). Anidium ion).

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

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

Examples of the substituent group include the same as _{R 1, R 2, P 1} , P 2, Q 1, substituents listed in represented by Q _2, and W in the general formula (1).

The alkyl group and aryl group of R ′ have the same meanings as the substituent examples given when R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W are alkyl groups or aryl groups.

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

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

When R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W represent a trivalent group, the trivalent group includes a trivalent hydrocarbon group, a trivalent heterocyclic group, N- or a combination thereof with a divalent group (for example,> NCH ₂ CH ₂ NH—,> NCONH—, etc.) is preferable.

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

  In the general formula (1), t represents the number of groups that can be bonded to the heterocyclic group, and preferred examples are 0, 1, 2, 3, or 4, particularly preferably 0 to 3, of which 0 to 2 is most preferred.

  In the general formula (1), preferable examples of the 5- to 6-membered heterocycle formed by G are a 5-membered or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group, Further, it may be condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms.

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

  More preferably, a pyridine ring, a pyrazine ring, a pyridazine ring, and a triazine ring are preferable, and among them, a pyridine ring, a pyrimidine ring, and a triazine ring are preferable, and among them, an S-triazine ring, a pyrimidine ring, a pyridazine ring, and a pyrazine ring are preferable, In particular, 2,3-pyridazine ring, 2,4-pyrimidine ring, 2,5-pyrazine ring, 2,6-pyrimidine ring, and s-triazine ring are most preferable.

When the heterocyclic group constituting G is a group that can further have a substituent, examples of the substituent include R ₁ , R ₂ , P ₁ , P ₂ , and the like in general formula (1). The same substituents as mentioned in Q ₁ , Q ₂ and W can be mentioned.

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

  A particularly preferable combination as the azo pigment represented by the general formula (1) of the present invention includes the following (A) to (H).

(I) G is preferably a 5- to 6-membered nitrogen-containing heterocycle, and examples thereof without limiting the substitution position include s-triazine group, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or A pyrrole ring is preferable, and among them, s-triazine ring, pyrimidine ring, pyridazine ring or pyrazine ring is preferable, and 2,3-pyridazine ring, 2,4-pyrimidine ring, 2,5-pyrazine ring, 2,6- Most preferred are a pyrimidine ring and an s-triazine ring.

(B) W is a hydroxyl group, a cyano group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio Group, a substituted or unsubstituted arylthio group is preferable, and a hydroxyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group is preferable, and among them, a hydroxyl group and an amino group are most preferable. .

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

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

(E) P ₁ , P ₂ , Q ₁ and Q ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or substituted or unsubstituted An unsubstituted arylsulfonyl group is preferable, and a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted acyl group is particularly preferable, and among them, a hydrogen atom is particularly preferable.

(F) Particularly preferable as X ₁ and X ₂ are each independently a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms. Among them, a cyano group or an alkylsulfonyl group having 1 to 12 carbon atoms is preferable, and a cyano group is most preferable.

(G) Y ₁ and Y ₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted group. A substituted C4-C12 heterocyclic group having a total carbon number is preferable, and among them, a hydrogen atom, a linear alkyl group having a total carbon number of C1-C8 or a branched alkyl group is preferable, and a hydrogen atom or a C1-C8 alkyl group is particularly preferable. Group is preferred, and a hydrogen atom is most preferred.

(H) G ₁ and G ₂ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, substituted or unsubstituted Are preferably an aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a particularly preferred substituent is a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group In particular, a substituted or unsubstituted heterocyclic group is preferable, and a substituted or unsubstituted nitrogen-containing heterocyclic group is most preferable.

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

Hereinafter, the azo pigment represented by the general formula (2), a tautomer thereof, a salt or a hydrate thereof will be described in detail.
General formula (2):

(In the general formula (2), X ₁ and X ₂ each independently represent an electron withdrawing group having a Hammett's σp value of 0.2 or more. Y ₁ , Y ₂ , G ₁ , G ₂ , R ₁ , R ₂ each independently represents a hydrogen atom or a substituent, G represents a nonmetallic atomic group capable of constituting a 5- to 6-membered heterocycle, and W represents a substituent that can be bonded to the heterocycle constituting G. T represents an integer of 0 to 4.)

Hereinafter, X ₁ , X ₂ , Y ₁ , Y ₂ , R ₁ , R ₂ , G, W, t, G ₁ and G ₂ will be described in more detail.

Examples of substituents for X ₁ and X ₂ are independently the same as the examples of X ₁ and X _{2 in} the general formula (1), and preferred examples are also the same.

Examples of substituents of Y ₁ and Y ₂ are independently the same as examples of Y ₁ and Y _{2 in} the general formula (1), and preferred examples are also the same.

Examples of substituents for R ₁ and R ₂ are independently the same as the examples of R ₁ and R _{2 in} the general formula (1), and preferred examples are also the same.

  Examples of the substituent of G are each independently the same as the example of G in the general formula (1), and preferred examples are also the same.

  Examples of the substituent of W are each independently synonymous with the example of W in the general formula (1), and preferred examples are also the same.

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

The heterocyclic groups represented by G ₁ and G ₂ are independently the same as the examples of G ₁ and G _{2 in} the general formula (1), and preferred examples are also the same.

  Regarding the preferred combination of substituents of the pigment represented by the general formula (2) of the present invention, a compound in which at least one of various substituents is the above-mentioned preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

  A particularly preferable combination as the azo pigment represented by the general formula (2) of the present invention includes the following (A) to (G).

(A) G is preferably a 5- to 6-membered nitrogen-containing heterocycle, and examples thereof without limiting the substitution position include s-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or A pyrrole ring is preferable, and among them, s-triazine ring, pyrimidine ring, pyridazine ring or pyrazine ring is preferable, and 2,3-pyridazine ring, 2,4-pyrimidine ring, 2,5-pyrazine ring, 2,6- Most preferred are a pyrimidine ring and an s-triazine ring.

(B) W is a hydroxyl group, a cyano group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio Group, a substituted or unsubstituted arylthio group is preferable, and a hydroxyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group is preferable, and among them, a hydroxyl group and an amino group are most preferable. .

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

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

(E) Particularly preferred as X ₁ and X ₂ are each independently a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms. Among them, a cyano group or an alkylsulfonyl group having 1 to 12 carbon atoms is preferable, and a cyano group is most preferable.

(F) Y ₁ and Y ₂ are each independently a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C18 aryl group, or a substituted or unsubstituted group. A substituted C4-C12 heterocyclic group having a total carbon number is preferable, and among them, a hydrogen atom, a linear alkyl group having a total carbon number of C1-C8 or a branched alkyl group is preferable, and a hydrogen atom or a C1-C8 alkyl group is particularly preferable. Group is preferred, and a hydrogen atom is most preferred.

(G) G ₁ and G ₂ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, substituted or unsubstituted Are preferably an aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a particularly preferred substituent is a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group In particular, a substituted or unsubstituted heterocyclic group is preferable, and a substituted or unsubstituted nitrogen-containing heterocyclic group is most preferable.

  The azo pigment represented by the general formula (2) is preferably an azo pigment represented by the following general formula (3).

  Hereinafter, the azo pigment represented by the general formula (3), a tautomer thereof, a salt or a hydrate thereof will be described in detail.

General formula (3):

In the general formula (3), X ₁ and X ₂ each independently represent an electron withdrawing group having a Hammett's σp value of 0.2 or more. Y ₁ , Y ₂ , G ₁ , G ₂ , R ₁ , R ₂ each independently represents a hydrogen atom or a substituent. G ′ represents a nonmetallic atomic group capable of constituting a 6-membered nitrogen-containing heterocycle. W represents a substituent that can be bonded to the heterocycle formed by G ′. t represents an integer of 0 to 4.

Hereinafter, X ₁ , X ₂ , Y ₁ , Y ₂ , R ₁ , R ₂ , G ′, W, t, G ₁ and G ₂ will be described in more detail.

Examples of substituents for X ₁ and X ₂ are independently the same as the examples of X ₁ and X _{2 in} the general formula (2), and preferred examples are also the same.

Examples of the substituent for Y ₁ and Y ₂ are independently the same as the examples of Y ₁ and Y _{2 in} the general formula (2), and preferred examples are also the same.

Examples of substituents for R ₁ and R ₂ are independently the same as those for R ₁ and R _{2 in} the general formula (2), and preferred examples are also the same.

The heterocyclic groups represented by G ₁ and G ₂ are independently the same as the examples of G ₁ and G _{2 in} the general formula (2), and preferred examples are also the same.

  G ′ represents a non-metallic atomic group capable of constituting a 6-membered nitrogen-containing heterocycle, and is exemplified by a s-triazine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, and a pyridine ring. Of these, s-triazine ring, pyrimidine ring, pyridazine ring or pyrazine ring is preferable, and 2,3-pyridazine ring, 2,4-pyrimidine ring, 2,5-pyrazine ring, 2,6-pyrimidine ring, s -The triazine ring is most preferred.

  W represents a substituent that can be bonded to the heterocyclic ring that G ′ comprises, and when there are a plurality of Ws, each independently represents a substituent. Examples of the substituent for W are each independently synonymous with the example of W in the general formula (2), and preferred examples are also the same.

  t represents the number of substituents W (an integer of 0 to 4) that can be bonded to the heterocyclic group formed by G ′, preferably an integer of 0 to 3, and particularly preferably 0 to 2, among them. 0 to 1 is most preferable.

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

  A particularly preferable combination as the azo pigment represented by the general formula (3) of the present invention includes the following (A) to (G).

(A) G ′ represents a 6-membered nitrogen-containing heterocycle, and is exemplified by without limiting the substitution position, and is preferably an s-triazine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, or a pyridine ring, and among them, an s-triazine Ring, pyrimidine ring, pyridazine ring or pyrazine ring is preferable, and 2,3-pyridazine ring, 2,4-pyrimidine ring, 2,5-pyrazine ring, 2,6-pyrimidine ring and s-triazine ring are most preferable. .

(B) W is a hydroxyl group, a cyano group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio Group, a substituted or unsubstituted arylthio group is preferable, and a hydroxyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group is preferable, and among them, a hydroxyl group and an amino group are most preferable. .

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

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

(E) Particularly preferred as X ₁ and X ₂ are each independently a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms. Among them, a cyano group or an alkylsulfonyl group having 1 to 12 carbon atoms is preferable, and a cyano group is most preferable.

(F) Y ₁ and Y ₂ are each independently a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C18 aryl group, or a substituted or unsubstituted group. A substituted C4-C12 heterocyclic group having a total carbon number is preferable, and among them, a hydrogen atom, a linear alkyl group having a total carbon number of C1-C8 or a branched alkyl group is preferable, and a hydrogen atom or a C1-C8 alkyl group is particularly preferable. Group is preferred, and a hydrogen atom is most preferred.

(G) G ₁ and G ₂ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, substituted or unsubstituted Are preferably an aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a particularly preferred substituent is a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group In particular, a substituted or unsubstituted heterocyclic group is preferable, and a substituted or unsubstituted nitrogen-containing heterocyclic group is most preferable.

  The azo pigment represented by the general formula (3) is preferably an azo pigment represented by the following general formula (4).

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

General formula (4):

(In the general formula (4), X ₁ and X ₂ each independently represents an electron withdrawing group having a Hammett's σp value of 0.2 or more. Y ₁ , Y ₂ , R ₁ and R ₂ are each independently Represents a hydrogen atom or a substituent, G ′ represents a non-metallic atomic group capable of constituting a 6-membered nitrogen-containing heterocycle, and W represents a substituent capable of bonding to the heterocycle constituting G ′. t represents an integer of 0 to 4. X ₁₁ and X ₁₂ each independently represents a heteroatom, and G ₁₁ and G ₁₂ each independently represent a nonmetallic atomic group for forming a heterocycle.

Hereinafter, the R ₁ , R ₂ , G ₁₁ , G ₁₂ , X ₁₁ , X ₁₂ , G ′, W, t, X ₁ , X ₂ , Y ₁ , Y ₂ will be described in more detail.

Examples of R _1, R ₂ are the same as examples of R _1, R ₂ each independently of the above general formula (3), and preferred examples are also the same.

  Examples of G ′ are independently the same as examples of G ′ in the general formula (3), and preferred examples are also the same.

  Examples of the substituent of W are each independently synonymous with the example of W in the general formula (3), and preferred examples are also the same.

  The example of t is synonymous with the example of t in the said General formula (3), and its preferable example is also the same.

Examples of X _1, X ₂ are the same as each independently of X _1, X ₂ in the general formula (3) in Example, and preferred examples are also the same.

Examples of Y _1, Y ₂ are the same as each independently of Y _1, Y ₂ in the general formula (3) in Example, and preferred examples are also the same.

X ₁₁ and X ₁₂ each independently represent a heteroatom in a non-metallic atomic group for forming a heterocyclic ring, and preferred examples are an N atom, an O atom, and an S atom. Among them, N atom is most preferable among them.

（上記一般式（５）中の（Ｇ−１）〜（Ｇ−１３）で表される＊は、上記一般式（４）で表されるピラゾール環上のＮ原子との結合部位を表す。Ｚ₁₁〜Ｚ₁₄はヘテロ環に結合可能な基を表す。（Ｇ−１３）中のＧ’’は、ヘテロ環を形成可能な非金属原子団を表す。） Preferred examples of G ₁₁ and G ₁₂ are each independently (G-1) to (G-13) in the following general formula (5).
General formula (5):

(* Represented by (G-1) to (G-13) in the general formula (5) represents a binding site with the N atom on the pyrazole ring represented by the general formula (4). Z _{11 to} Z ₁₄ each represent a group that can be bonded to a heterocycle. G ″ in (G-13) represents a nonmetallic atomic group that can form a heterocycle.)

In the general formula (5), preferred examples of Z ₁₁ , Z ₁₂ , Z ₁₃ and Z ₁₄ in (G-1) to (G-13) are a hydrogen atom or Y ₁ in the general formula (1), Y ₂ , R ₁ , R ₂ , G ₁ , G ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ and W are synonymous with the substituents, and preferred examples are also the same.

Examples of the heterocyclic ring represented by G ′ in (G-13) in the above general formula (5) are 5 to 6-membered heterocyclic rings constituted by G ₁ in the above general formula (3) as much as possible to form a condensed ring. The preferred examples are the same, and the preferred examples are also the same.

  Regarding the preferred combination of substituents of the pigment represented by the general formula (4) of the present invention, a compound in which at least one of various substituents is the above preferred group is preferred, and more various substituents are preferred. More preferred are compounds that are groups, and most preferred are compounds in which all substituents are the preferred groups.

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

(A) G ′ represents a 6-membered nitrogen-containing heterocycle, and is exemplified by without limiting the substitution position, and is preferably an s-triazine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, or a pyridine ring, and among them, an s-triazine Ring, pyrimidine ring, pyridazine ring or pyrazine ring is preferable, and 2,3-pyridazine ring, 2,4-pyrimidine ring, 2,5-pyrazine ring, 2,6-pyrimidine ring and s-triazine ring are most preferable. .

(B) W is a hydroxyl group, a cyano group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio Group, a substituted or unsubstituted arylthio group is preferable, and a hydroxyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group is preferable, and among them, a hydroxyl group and an amino group are most preferable. .

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

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

(E) Particularly preferred as X ₁ and X ₂ are each independently a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms. Among them, a cyano group or an alkylsulfonyl group having 1 to 12 carbon atoms is preferable, and a cyano group is most preferable.

(F) Y ₁ and Y ₂ are each independently a hydrogen atom, a substituted or unsubstituted C1-C12 alkyl group, a substituted or unsubstituted C6-C18 aryl group, or a substituted or unsubstituted group. A substituted C4-C12 heterocyclic group having a total carbon number is preferable, and among them, a hydrogen atom, a linear alkyl group having a total carbon number of C1-C8 or a branched alkyl group is preferable, and a hydrogen atom or a C1-C8 alkyl group is particularly preferable. Group is preferred, and a hydrogen atom is most preferred.

(G) X ₁₁ and X ₁₂ each independently represent a hetero atom, and preferred examples include an N atom, an O atom, and an S atom, particularly an N atom and an O atom, and an N atom is most preferred.

(H) Particularly preferred as G ₁₁ and G ₁₂ are each independently (G-1), (G-2), (G-3), (G-4), (G -5), (G-6), (G-7), (G-9), (G-10), and (G-11) are preferred. Among them, particularly preferred substituents are (G-1), (G-2), (G-3), (G-4), (G-5), and (G-6) are preferable, and in particular, (G-1), (G-3), (G-4) ), (G-5) and (G-6) are preferred, and (G-1), (G-4) and (G-6) are most preferred.

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

The present invention includes in its scope tautomers of the azo pigments represented by the general formulas (1) to (5). Although the general formulas (1) to (5) are shown in the form of an extreme structural formula among several tautomers that can be taken from the chemical structure, they are tautomers other than the described structures. It may be used as a mixture containing a plurality of tautomers.
For example, the pigment represented by the general formula (2) may be an azo-hydrazone tautomer represented by the following general formula (2 ′).
The present invention includes in its scope a compound represented by the following general formula (2 ′), which is a tautomer of the azo pigment represented by the general formula (2).

(In the general formula (2 ′), X ₁ , X ₂ , Y ₁ , Y ₂ , R ₁ , R ₂ , G ₁ , G ₂ , P ₁ , P ₂ , Q ₁ , Q ₂ , G, W and t Is synonymous with that defined in general formula (2).)

In the present invention, the azo pigments represented by the general formulas (1) to (5) may contain, for example, a tautomer represented by the above extreme structural formula. The main component is preferably one selected from pigments, salts thereof, hydrates and tautomers thereof. That is, it is preferable that the content of the azo pigment represented by a single ultimate structural formula is the main component, and the azo pigment represented by a different ultimate structure is small. 70% to 100%, preferably 80% to 100%, more preferably 90% to 100%, still more preferably 95% to 100, particularly preferably 100%. By using an azo pigment represented by a single limit structural formula as the main component, the regularity of the dye molecules is improved, and intramolecular and intermolecular interactions are strengthened to form higher-order three-dimensional networks. It is preferable in terms of performance required for the pigment, such as improvement in hue, light fastness, heat fastness, humidity fastness, oxidizing gas fastness and solvent resistance.
The mixing ratio of azo pigments, salts, hydrates and tautomers thereof is as follows: single crystal X-ray crystal structure analysis, powder X-ray diffraction (XRD), crystal micrograph (TEM), IR (KBr method) It can confirm from the physicochemical measurement value of solids, such as.

  Many tautomers can be considered in the azo pigments represented by the general formulas (1) to (5). Among the azo pigments represented by the general formulas (1) to (5), as described above, examples of the particularly preferable general azo pigments include the azo pigments represented by the following general formulas (6) and (7). Can be mentioned.

  The reason why this structure is preferable is that a nitrogen atom, a hydrogen atom, and a hetero atom (oxygen atom of the carbonyl group or amino group) constituting the heterocycle contained in the azo pigment structure as represented by the general formulas (6) and (7) (Nitrogen atom) can easily form at least one cross-over hydrogen bond (intramolecular hydrogen bond) in the molecule. As a result, the planarity of the molecule is improved, the intramolecular / intermolecular interaction is further improved, and the crystallinity of the azo pigments represented by the general formulas (6) and (7) is increased (a higher-order structure is formed). This is the most preferable example because the light fastness, thermal stability, wet heat stability, water resistance, gas resistance and / or solvent resistance, which are required performance as a pigment, are greatly improved.

(In the general formulas (6) and (7), X ₁ , X ₂ , Y ₁ , Y ₂ , R ₁ , R ₂ , G ₁ , G ₂ , and G ′ are as defined in the general formula (2)). Synonymous.)

  Specific examples of the azo pigments represented by the general formulas (1) to (5) (exemplary azo pigments Pig-1 to Pig- ??) are shown below. The azo pigments used in the present invention are the following examples. It is not limited to.

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

  The pigment represented by the general formulas (1) to (5) of the present invention may have any chemical form as long as the chemical structural formula is the general formula (1) to (5) or a tautomer thereof, and is also referred to as polymorph. It may be a pigment.

Crystal polymorphs refer to the same chemical composition but different arrangement of building blocks (molecules or ions) in the crystal. The crystal structure determines the chemical and physical properties, and each polymorph can be distinguished by its rheology, color, and other color characteristics. Different polymorphs can also be confirmed by X-Ray Diffraction (powder X-ray diffraction measurement results) and X-Ray Analysis (X-ray crystal structure analysis results).
When the crystalline polymorph is present in the pigments represented by the general formulas (1) to (5) of the present invention, any polymorph may be used, and a mixture of two or more polymorphs may be used. The main component is preferably a single crystal type. That is, it is preferable that the polycrystal system is not mixed, and the content of the azo pigment having a single crystal type is 70% to 100%, preferably 80% to 100%, more preferably 90% with respect to the entire azo pigment. -100%, more preferably 95% -100, particularly preferably 100%. By using an azo pigment having a single crystal form as a main component, the regularity of the dye molecule arrangement is improved, the intramolecular / intermolecular interaction is strengthened, and a higher-order three-dimensional network can be easily formed. Therefore, it is preferable in terms of performance required for the pigment, such as improvement in hue, light fastness, heat fastness, humidity fastness, oxidizing gas fastness and solvent resistance.
The mixing ratio of crystal polymorphs in azo pigments is based on solid physicochemical measurements such as single crystal X-ray crystal structure analysis, powder X-ray diffraction (XRD), crystal micrograph (TEM), IR (KBr method), etc. I can confirm.

  In the present invention, when the azo pigments represented by the general formulas (1) to (5) have an acid group, part or all of the acid group may be in a salt form. These pigments and free acid type pigments may be mixed. Examples of the salt type include salts of alkali metals such as Na, Li and K, ammonium salts optionally substituted with an alkyl group or hydroxyalkyl group, and organic amine salts. Examples of organic amines include lower alkyl amines, hydroxy-substituted lower alkyl amines, carboxy-substituted lower alkyl amines, and polyamines having 2 to 10 alkyleneimine units having 2 to 4 carbon atoms. In the case of these salt types, the type is not limited to one type, and a plurality of types may be mixed.

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

  In the present invention, the azo pigments represented by the general formulas (1) to (5) may be hydrates containing water molecules in the crystals.

  In the present invention, for example, the azo pigments represented by the above general formulas (1) to (5) have various tautomers and / or crystal polymorphs, and an absorption pattern in an infrared absorption spectrum, for example, depends on the form. Different.

  The azo pigment represented by the general formula (1) can be produced by the following method.

That is, the heterocyclic amine represented by the following general formula (I) is diazoniumized, and subsequently subjected to a coupling reaction with the compound represented by the following general formula (II), thereby being represented by the above general formula (1). Azo pigments can be produced.
Formula (I):

(In the formula, X ₁ , X ₂ , Y ₁ , Y ₂ , G, W, t are X ₁ , X ₂ , Y of the hetero ring part in the azo pigment structure represented by the above general formula (1). ₁ , Y ₂ and G are synonymous.)

In the general formula (I), X ₁ and X ₂ are synonymous with X ₁ and X ₂ represented by the general formula (1), and preferred examples are also the same.

In the general formula (I), Y ₁ and Y ₂ have the same meanings as Y ₁ and Y ₂ represented by the general formula (1), and preferred examples are also the same.
In general formula (I), G is synonymous with the example of G in the said general formula (1), and its preferable example is also the same.

  In general formula (I), W is synonymous with the example of W in the said general formula (1), and its preferable example is also the same.

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

General formula (II):

  In the formula, R, P and Q each independently represent a hydrogen atom or a monovalent substituent. G represents a nonmetallic atomic group capable of constituting a 5- to 6-membered heterocycle.

In general formula (II), R, P and Q have the same meanings as R ₁ , R ₂ , P ₁ , P ₂ , Q ₁ and Q ₂ represented by general formula (1), and preferred examples are also the same. It is.

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

  Particularly preferred combinations as intermediates of the azo pigments represented by the general formula (I) and general formula (II) of the present invention include the following (A) to (H).

(A) G is preferably a 5- to 6-membered nitrogen-containing heterocycle, and examples thereof without limiting the substitution position include s-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, or A pyrrole ring is preferable, and among them, an s-triazine ring, a pyrimidine ring, a pyridazine ring, or a pyrazine ring is preferable, and in particular, between 2,3-pyridazine, 2,4-pyrimidine ring, 2,5-pyrazine ring, 2,6- Most preferred are a pyrimidine ring and an s-triazine ring.

(B) W is a hydroxyl group, a cyano group, a substituted or unsubstituted carbamoyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted alkylthio Group, a substituted or unsubstituted arylthio group is preferable, and a hydroxyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group is preferable, and among them, a hydroxyl group and an amino group are most preferable. .

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

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

(E) P ₁ , P ₂ , Q ₁ and Q ₂ are each independently a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted acyl group, a substituted or unsubstituted alkylsulfonyl group, or substituted or unsubstituted An unsubstituted arylsulfonyl group is preferable, and a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted acyl group is particularly preferable, and among them, a hydrogen atom is particularly preferable.

(F) Particularly preferable as X ₁ and X ₂ are each independently a cyano group, an alkylsulfonyl group having 1 to 12 carbon atoms, an arylsulfonyl group having 6 to 18 carbon atoms, or a sulfamoyl group having 0 to 12 carbon atoms. Among them, a cyano group or an alkylsulfonyl group having 1 to 12 carbon atoms is preferable, and a cyano group is most preferable.

(G) Y ₁ and Y ₂ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group having a total carbon number of C1 to C12, a substituted or unsubstituted aryl group having a total carbon number of C6 to C18, or a substituted or unsubstituted group. A substituted C4-C12 heterocyclic group having a total carbon number is preferable, and among them, a hydrogen atom, a linear alkyl group having a total carbon number of C1-C8 or a branched alkyl group is preferable, and a hydrogen atom or a C1-C8 alkyl group is particularly preferable. Group is preferred, and a hydrogen atom is most preferred.

(H) G ₁ and G ₂ are a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted cycloalkyl group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkynyl group, substituted or unsubstituted Are preferably an aralkyl group, a substituted or unsubstituted aryl group, or a substituted or unsubstituted heterocyclic group, and among them, a particularly preferred substituent is a substituted or unsubstituted aryl group, a substituted or unsubstituted heterocyclic group In particular, a substituted or unsubstituted heterocyclic group is preferable, and a substituted or unsubstituted nitrogen-containing heterocyclic group is most preferable.

  Below, it demonstrates in detail regarding the synthesis | combination of the azo pigment of this invention.

  The azo pigment of the present invention can be synthesized, for example, by subjecting a diazonium salt prepared by a known method to a diazo component of the general formula (I) and an azo coupling reaction of the coupling component of the general formula (II).

  The diazonium salt preparation and coupling reaction can be carried out by conventional methods.

  Preparation of the diazonium salt of the general formula (I) can be carried out, for example, in a reaction medium containing an acid (eg hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, methanesulfonic acid, trifluoromethanesulfonic acid, etc.) Conventional diazonium salt preparation methods using nitrous acid, nitrite or nitrosylsulfuric acid can be applied.

  More preferred examples of the acid include a case where acetic acid, propionic acid, methanesulfonic acid, phosphoric acid and sulfuric acid are used alone or in combination, and among them, phosphoric acid or a combined system of acetic acid and sulfuric acid is particularly preferred.

  Preferable examples of the reaction medium (solvent) include organic acids and inorganic acids, and phosphoric acid, sulfuric acid, acetic acid, propionic acid, and methanesulfonic acid are particularly preferable. Among these, acetic acid and / or propionic acid are preferable.

  As an example of a preferable nitrosonium ion source, a diazonium salt can be stably and efficiently prepared by using nitrosylsulfuric acid in the above-mentioned preferable acid-containing reaction medium.

  0.5-50 mass times is preferable, as for the usage-amount of the solvent with respect to the diazo component of general formula (I), More preferably, it is 1-20 mass times, and 3-10 mass times is especially preferable.

  In the present invention, the diazo component of the general formula (I) may be dispersed in a solvent, or may be in the form of a solution depending on the type of diazo component.

  The amount of nitrosonium ion source used is preferably 0.95 to 5.0 equivalents, more preferably 1.00 to 3.00 equivalents, particularly 1.00 to 1.10 equivalents, relative to the diazo component. Is preferred.

  The reaction temperature is preferably -15 ° C to 30 ° C, more preferably -10 ° C to 10 ° C, and further preferably -5 ° C to 5 ° C. Less than −10 ° C. is not economical because the reaction rate is remarkably slow and the time required for the synthesis is remarkably increased, and it is preferable to synthesize at a high temperature exceeding 30 ° C. because the amount of by-products increases. Absent.

  The reaction time is preferably 30 minutes to 300 minutes, more preferably 30 minutes to 200 minutes, and still more preferably 30 minutes to 150 minutes.

  The coupling reaction can be carried out in an acidic reaction medium to a basic reaction medium, but the azo pigment of the present invention is preferably carried out in an acidic to neutral reaction medium, particularly in an acidic reaction medium. This suppresses the decomposition of the diazonium salt and can efficiently induce the azo pigment.

  As a preferable example of the reaction medium (solvent), an organic acid, an inorganic acid, or an organic solvent can be used, but an organic solvent is particularly preferable, and a solvent that does not cause a liquid separation phenomenon during the reaction and presents a uniform solution with the solvent. preferable. For example, alcoholic organic solvents such as methanol, ethanol, propanol, isopropanol, butanol, t-butyl alcohol, amyl alcohol, ketone organic solvents such as acetone, methyl ethyl ketone, ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene Diol-based organic solvents such as glycol and 1,3-propanediol, ether-based organic solvents such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, and ethylene glycol diethyl ether, tetrahydrofuran, dioxane, acetonitrile, and the like. May be a mixture of two or more.

  Preferably, the organic solvent has a polarity parameter (ET) value of 40 or more. Among them, a glycol solvent having two or more hydroxyl groups in the solvent molecule, or an alcohol solvent having 3 or less carbon atoms, preferably an alcohol solvent having 2 or less carbon atoms (for example, methanol, ethylene glycol) is used. preferable. These mixed solvents are also included.

  The amount of the solvent used is preferably 1 to 100 times by mass, more preferably 1 to 50 times by mass, and even more preferably 2 to 10 times by mass of the coupling component represented by the general formula (II).

  In the present invention, the coupling component of the general formula (II) may be in a state of being dispersed in a solvent, or may be in a state of a solution depending on the type of the coupling component.

  The amount of the coupling component used is preferably 0.95 to 5.0 equivalents, more preferably 1.00 to 3.00 equivalents, particularly 1.00 to 1.50, based on the azo coupling site. It is preferable that it is equivalent.

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

  The reaction time is preferably 30 minutes to 300 minutes, more preferably 30 minutes to 200 minutes, and still more preferably 30 minutes to 150 minutes.

  In the method for synthesizing azo pigments of the present invention, the product (crude azo pigment) obtained by these reactions may be subjected to a normal organic synthesis reaction post-treatment method and then purified or used without purification. it can.

  That is, for example, the product liberated from the reaction system can be used without being purified, or can be purified by recrystallization, salt formation, etc., alone or in combination.

  After completion of the reaction, the reaction solvent is distilled off, or it is poured into water or ice without being distilled off, and the liberated product is extracted with neutralization or without neutralization, or extracted with an organic solvent / aqueous solution. It can also be used after purification or refining by recrystallization, crystallization, salt formation or the like, either alone or in combination.

  The method for synthesizing the azo pigment of the present invention will be described in more detail.

  The method for producing an azo pigment of the present invention includes a coupling reaction of a diazonium compound obtained by diazonium-izing a heterocyclic amine represented by the above general formula (I) and a compound represented by the above general formula (II). The coupling reaction can be carried out after dissolving the compound of general formula (II) in an organic solvent.

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

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

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

  Α-type crystals can also be produced efficiently by a method in which a coupling reaction is carried out in the presence of a polar aprotic solvent. Examples of polar aprotic solvents include N, N-dimethylformamide, N, N-dimethylacetamide, N-methyl-2-pyrrolidone, dimethyl sulfoxide, tetramethylurea, and mixed solvents thereof. When these solvents are used, the compound of the above general formula (II) may or may not be completely dissolved in the solvent.

  Although the compounds represented by the above general formulas (1) to (5) are obtained as crude azo pigments (crude) by the above production method, it is desirable to perform post-treatment when used as the pigment of the present invention. Examples of post-treatment methods include solvent salt milling, salt milling, dry milling, solvent milling, pigment particle control step by grinding treatment such as acid pasting, solvent heating treatment, resin, surfactant and dispersant. The surface treatment process by etc. is mentioned.

The compounds represented by the general formulas (1) to (5) of the present invention are preferably subjected to solvent heat treatment and / or solvent salt milling as a post-treatment.
Examples of the solvent used in the solvent heat treatment include water, aromatic hydrocarbon solvents such as toluene and xylene, halogenated hydrocarbon solvents such as chlorobenzene and o-dichlorobenzene, and alcohols such as isopropanol and isobutanol. Examples thereof include solvents, polar aprotic organic solvents such as N, N-dimethylformamide, N, N-dimethylacetamide, and N-methyl-2-pyrrolidone, glacial acetic acid, pyridine, and mixtures thereof. An inorganic or organic acid or base may be further added to the solvents mentioned above. The temperature of the solvent heat treatment varies depending on the desired primary particle size of the pigment, but is preferably 40 to 150 ° C, more preferably 60 to 100 ° C. The treatment time is preferably 30 minutes to 24 hours.

  As solvent salt milling, for example, a crude azo pigment, an inorganic salt, and an organic solvent that does not dissolve the crude azo pigment are charged into a kneader and kneaded and ground therein. As 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 is characterized by containing at least one azo pigment represented by the general formulas (1) to (5). Thereby, it can be set as the pigment dispersion excellent in chromatic characteristics, durability, and dispersion stability.

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

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

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

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

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

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

  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.

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

  A more preferable volume average particle diameter is 20 nm or more and 250 nm or less, and further preferably 30 nm or more and 230 nm or less. When the number average particle size of the particles in the pigment dispersion is less than 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 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.

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

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

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

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

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

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

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

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

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

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

  The pigment of the present invention is preferably contained in an amount of 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass in 100 parts by mass of the ink of the present invention. It is more preferable to contain 10 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 applicable magenta pigments include C.I. I. P. V. -19, C.I. I. P. R. -122, and examples of applicable cyan pigments include C.I. I. P. B. -15: 3, C.I. I. P. B. -15: 4 can be mentioned, and apart from these, any one can be used. Applicable black materials include disazo, trisazo, and tetraazo pigments, as well as carbon black dispersions.

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

  The viscosity of the ink is preferably from 1.2 mPa · s to 8.0 mPa · s, more preferably from 1.5 mPa · s to less than 6.0 mPa · s, still more preferably from 1.8 mPa · s to 4. It is less than 5 mPa · s. When the viscosity is greater than 8.0 mPa · s, the dischargeability may be reduced. On the other hand, when it is smaller than 1.2 mPa · s, the long-term jetting property may deteriorate.

The viscosity (including those described later) was measured using a rotational viscometer Rheomat 115 (manufactured by Contraves) at 23 ° C. and a shear rate of 1400 s ⁻¹ .

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

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

  In order to adjust conductivity and pH, compounds of alkali metals such as potassium hydroxide, sodium hydroxide, lithium hydroxide, ammonium hydroxide, triethanolamine, diethanolamine, ethanolamine, 2-amino-2-methyl Nitrogen-containing compounds such as -1-propanol, alkaline earth metal compounds such as calcium hydroxide, acids such as sulfuric acid, hydrochloric acid and nitric acid, strong acid and weak alkali salts such as ammonium sulfate, and the like can be used.

  In addition, a pH buffer, an antioxidant, a fungicide, a viscosity modifier, a conductive agent, an ultraviolet absorber, and the like can be added as necessary.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

(1) Synthesis of compound (Cp-1):
24.2 g of pivaloylacetonitrile (manufactured by Tokyo Chemical Industry) was added in portions to 20.0 g of compound (b-1) (manufactured by Wako Pure Chemical Industries) and 80 mL of ethanol solution at room temperature, and the internal temperature was raised to 70 ° C. And refluxed for 15.0 hours. Subsequently, the mixture was allowed to cool to room temperature, and ethanol was distilled off with an evaporator. Thereafter, 40 mL of isopropyl alcohol was added to cool to an internal temperature of 4 ° C. and stirred for 0.5 hour, followed by filtration. The crystals were washed with 40 mL of isopropyl alcohol, and the obtained crystals were dried at 60 ° C. for 3 hours to obtain 14.3 g of compound (Cp-1).
¹ H-NMR (DMSO-d6), δ value TMS standard: 1.21 to 1.25 (9H, s), 5.28 to 5.34 (1H, s), 6.67 to 6.73 (2H , S), 7.12 to 7.20 (1H, t), 7.78 to 7.82 (1H, d), 7.83 to 7.92 (1H, t), 8.32 to 8.38. (1H, t))

(2) Synthesis of compound (B):
A solution of 63.0 g of hydrazine monohydrate (manufactured by Wako Pure Chemical Industries, Ltd.) and 50 mL of ethanol was adjusted to an internal temperature of 10 ° C., and 25.0 g of compound (A) (manufactured by Wako Pure Chemical Industries, Ltd.) was added in portions and 0 at the same temperature. Stir for 5 hours. Thereafter, the internal temperature was raised to 50 ° C. and stirred for 4.5 hours. Subsequently, the mixture was allowed to cool to room temperature, and 130 mL of water was added, followed by filtration and washing with 50 mL of water and isopropyl alcohol. The obtained crystals were dried at room temperature for 8 hours to obtain 21.6 g of compound (B).
¹ H-NMR (DMSO-d6), δ value TMS standard: 4.08 to 4.15 (4H, brs), 5.97 to 6.02 (1H, s), 7.52 to 7.59 (2H , Brs), 7.78-7.82 (1H, s))

(3) Synthesis of compound (D-1):
In a suspension of 10.0 g of compound (B) and 50 mL of methanol, 21.8 g of ethoxymethylenemalononitrile (manufactured by ARDRICH) was added in portions at room temperature, and 1N hydrochloric acid was added dropwise to adjust the pH to 3. Subsequently, the internal temperature was raised to 60 ° C. and stirred at the same temperature for 1.5 hours. Thereafter, the mixture was allowed to cool to room temperature, filtered, and washed with 30 mL of water and 30 mL of isopropyl alcohol. The obtained crystals were dried at 60 ° C. for 3 hours to obtain 18.8 g of compound (D-1).
¹ H-NMR (DMSO-d6), δ value TMS standard: 8.00 to 8.03 (1H, d), 8.21 to 8.26 (2H, s), 8.30 to 8.42 (4H , Brs), 8.93-8.97 (1H, s))

(4) Synthesis of Pig-1:
1.0 g of (D-1) was added to 30 mL phosphoric acid and 5 mL sulfuric acid mixed solution and heated to 50 ° C. to dissolve. This solution was ice-cooled and kept at −3 ° C., 0.59 g of sodium nitrite was added and stirred for 1 hour to obtain a diazonium salt solution. A suspension obtained by adding 2.2 g of (Cp-1) to 80 mL of methanol was prepared, and the above diazonium salt solution was added thereto at 2 to 10 ° C. over 10 minutes. The reaction was continued for 1 hour at 10 ° C., and the resulting powder was filtered off. This powder was added to 200 mL of water, and excess acid was neutralized with an aqueous potassium hydroxide solution. Filtration was performed again to obtain a yellow powder. This powder was added to a mixed solvent of 20 mL of N, N-dimethylacetamide and 20 mL of water and aged by heating at 85 ° C. for 4 hours. This aging solution was filtered while hot, and further washed with 80 mL of methanol to obtain 1.3 g of a reddish yellow solid (Pig-1).
MALDI-TOF-MS: 746.33 [M + H ⁺ ]

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

[Example 2]
5 parts of pigment (Pig-1) synthesized in Synthesis Example 1, and methacrylic acid-methacrylic acid ester copolymer represented by Dispersant Solution 10 described on page 22 of International Publication No. WO06 / 064193 as a polymeric dispersant 25.5 parts of the combined aqueous solution and 19.5 parts of water were mixed and dispersed for 6 hours at 300 rpm with a planetary ball mill together with 100 parts of zirconia beads having a diameter of 0.1 mm. After completion of the dispersion, the zirconia beads were separated to obtain a yellow pigment dispersion 2.

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

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

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

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

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

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

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

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

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

  As is clear from the results in Table 1, pigment dispersions 1 to 5 using the pigment of the present invention are excellent in color tone and exhibit high coloring power and light resistance.

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

Claims (8)

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

(In the general formula (1), X ₁ and X ₂ each independently represents an electron withdrawing group having a Hammett's σp value of 0.2 or more. Y ₁ , Y ₂ , R ₁ , R ₂ , G ₁ , G ₂ , P ₁ , P ₂ , Q ₁ and Q ₂ each independently represents a hydrogen atom or a substituent, G represents a nonmetallic atomic group capable of constituting a 5- to 6-membered heterocycle, W is And represents a substituent that can be bonded to the heterocycle formed by G. t represents an integer of 0 to 4.) The azo pigment represented by the general formula (1) is an azo pigment represented by the following general formula (2), a salt thereof, a hydrate thereof, and the like Tautomers of.
General formula (2)

(In the general formula (2), X ₁ and X ₂ each independently represent an electron withdrawing group having a Hammett's σp value of 0.2 or more. Y ₁ , Y ₂ , G ₁ , G ₂ , R ₁ , R ₂ each independently represents a hydrogen atom or a substituent, G represents a nonmetallic atomic group capable of constituting a 5- to 6-membered heterocycle, and W represents a substituent that can be bonded to the heterocycle constituting G. T represents an integer of 0 to 4.) The azo pigment according to claim 1 or 2, wherein the azo pigment represented by the general formula (1) or (2) is an azo pigment represented by the following general formula (3): Hydrates and their tautomers.
General formula (3)

(In the general formula (3), X ₁ and X ₂ each independently represents an electron withdrawing group having a Hammett's σp value of 0.2 or more. Y ₁ , Y ₂ , G ₁ , G ₂ , R ₁ , R ₂ each independently represents a hydrogen atom or a substituent, G ′ represents a non-metallic atomic group capable of constituting a 6-membered nitrogen-containing heterocycle, and W can be bonded to the heterocycle constituting G ′. And t represents an integer of 0 to 4.) The azo pigment according to claim 1 or 2, wherein the azo pigment represented by the general formula (1), (2) or (3) is an azo pigment represented by the following general formula (4). Pigments, their salts, hydrates and their tautomers.
General formula (4)

(In the general formula (4), X ₁ and X ₂ each independently represents an electron withdrawing group having a Hammett's σp value of 0.2 or more. Y ₁ , Y ₂ , R ₁ and R ₂ are each independently Represents a hydrogen atom or a substituent, G ′ represents a non-metallic atomic group capable of constituting a 6-membered nitrogen-containing heterocycle, and W represents a substituent capable of bonding to the heterocycle constituting G ′. t represents an integer of 0 to 4. X ₁₁ and X ₁₂ each independently represents a heteroatom, and G ₁₁ and G ₁₂ each independently represent a nonmetallic atomic group for forming a heterocycle. In the azo pigment represented by the general formula (4), the nitrogen-containing heterocycle represented by G ₁₁ and G ₁₂ is at least one selected from (G-1) to (G-13) in the following general formula (5). The azo pigment according to any one of claims 1 to 4, a salt, a hydrate, and a tautomer thereof, which are seeds.
General formula (5):

(* Represented by (G-1) to (G-13) in the general formula (5) represents a binding site with the N atom on the pyrazole ring represented by the general formula (4). Z _{11 to} Z ₁₄ each represent a group that can be bonded to a heterocycle. G ″ in (G-13) represents a nonmetallic atomic group that can form a heterocycle.)   A pigment dispersion comprising at least one azo pigment according to any one of claims 1 to 5, a salt, a hydrate thereof, and a tautomer thereof.   A coloring composition comprising at least one of the azo pigment according to any one of claims 1 to 5, a salt, a hydrate thereof, and a tautomer thereof.   An ink for ink-jet recording comprising at least one of the azo pigment according to any one of claims 1 to 5, its salt, hydrate, and tautomers thereof.