JP5745235B2 - Method for producing azo pigment - Google Patents

Description

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

  In recent years, a material for forming a color image has been mainly used as an image recording material, and specifically, an ink jet recording material, a thermal transfer recording material, an electrophotographic recording material, a transfer halogen. Silver halide photosensitive materials, printing inks, recording pens, and the like are actively used. Further, a color filter is used for recording and reproducing a color image on an image pickup device such as a CCD in a photographing apparatus and on an LCD or PDP in a display. In these color image recording materials and color filters, three primary colors (dyes and pigments) of the so-called additive color mixing method and subtractive color mixing method are used to display or record full color images. The fact is that there are no fast-acting dyes that have absorption characteristics that can satisfy the above conditions and that can withstand various use conditions and environmental conditions, and improvements are 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 further substantially insoluble in water and organic solvents and has good chemical fastness, and even when used as particles, the preferred absorption characteristics in the molecular dispersion state are impaired. It is also necessary to have properties such as absence. The required characteristics can be controlled by the strength of intermolecular interaction, but it is difficult to achieve both because they are in a trade-off relationship.
In addition, when using the pigment, in addition to exhibiting the desired transparency or concealing property, the fine particles are dispersed in the medium to be used, and the dispersion state is stable, etc. Properties are also required. Since these properties are greatly influenced not only by the chemical structure but also by the particle diameter, 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.

  As such a pigment, Patent Document 1 describes an azo pigment having a specific chemical structure. However, the production methods described in the examples of the patent document are not always efficient because the filterability is poor or filtration leakage occurs particularly when the azo pigment is separated from the reaction solution.

  Various methods for synthesizing azo compounds have been known for a long time, including synthesis by oxidation reaction, synthesis by reduction reaction, synthesis by substitution reaction, synthesis by addition reaction, synthesis by condensation reaction, and other synthesis methods. (See Non-Patent Document 1, for example). However, it is used as an industrial production method for azo compounds by reacting diazonium compounds with coupling components such as anilines and phenols from the viewpoint of availability of raw materials, cost, yield, etc. There are almost all methods for synthesis, and this method also has drawbacks such as the danger of explosion of the diazonium compound, and a low yield depending on the type of the diazonium compound and the coupling component. In particular, heterocyclic diazonium compounds are often unstable, and a highly general synthesis method is not known.

  Patent Document 2 describes a production method for obtaining an azo compound using a diazonium compound of pyrazole in high yield and high purity. However, a method capable of producing an azo pigment more efficiently is desired.

JP 2010-31224 A JP 2007-217681 A

New Experimental Chemistry Course (Maruzen Co., Ltd.), Volume 14-III, pages 1516 to 1534

  The present invention has been made paying attention to the above-mentioned problems in the method for producing an azo pigment, and can be used to produce an azo pigment having a specific chemical structure with high efficiency. It aims at providing the azo pigment obtained.

（一般式（２）中、Ｒ_１、Ｒ_２は、それぞれ独立に、水素原子、ハロゲン原子、アルキル基、シクロアルキル基、アラルキル基、アルケニル基、アルキニル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、アルコキシ基、アリールオキシ基、シリルオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルファモイル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、シリル基、アゾ基、イミド基、ホスホリル基、スルホ基、カルボキシル基、ホスホノ基又は４級アンモニウム基を表す。Ｇは５〜６員ヘテロ環基を表す。Ｗは、Ｇが構成するヘテロ環基に結合可能な置換基を表す。前記Ｇが構成するヘテロ環基に結合可能な置換基は、ハロゲン原子、アルキル基、シクロアルキル基、アラルキル基、アルケニル基、アルキニル基、アリール基、ヘテロ環基、シアノ基、ヒドロキシル基、ニトロ基、アルコキシ基、アリールオキシ基、シリルオキシ基、ヘテロ環オキシ基、アシルオキシ基、カルバモイルオキシ基、アルコキシカルボニルオキシ基、アリールオキシカルボニルオキシ基、アミノ基、アシルアミノ基、アミノカルボニルアミノ基、アルコキシカルボニルアミノ基、アリールオキシカルボニルアミノ基、スルファモイルアミノ基、アルキルスルホニルアミノ基、アリールスルホニルアミノ基、アルキルチオ基、アリールチオ基、ヘテロ環チオ基、スルファモイル基、アルキルスルフィニル基、アリールスルフィニル基、アルキルスルホニル基、アリールスルホニル基、アシル基、アリールオキシカルボニル基、アルコキシカルボニル基、カルバモイル基、ホスフィノ基、ホスフィニル基、ホスフィニルオキシ基、ホスフィニルアミノ基、シリル基、アゾ基、イミド基、ホスホリル基、スルホ基、カルボキシル基、ホスホノ基又は４級アンモニウム基を表す。ｔは０〜３の整数を表す。）
＜２＞
さらに、前記工程（ａ）で得たジアゾニウム化合物とカップリング成分とを混合して反応させる工程（ｂ）を含むことを特徴とする＜１＞に記載のアゾ顔料の製造方法。
＜３＞
さらに、工程（ｂ）で得た反応液に水を加える工程（ｃ）を含むことを特徴とする＜２＞に記載のアゾ顔料の製造方法。
＜４＞
前記工程（ａ）における混合が２０℃〜５０℃で行われることを特徴とする＜１＞〜＜３＞のいずれかに記載のアゾ顔料の製造方法。
＜５＞
前記アゾ顔料が下記式（３）で表されるアゾ顔料であることを特徴とする＜１＞〜＜４＞のいずれかに記載のアゾ顔料の製造方法。

＜６＞
前記酸塩が硫酸塩であることを特徴とする＜１＞〜＜５＞のいずれかに記載のアゾ顔料の製造方法。
＜７＞
前記酸塩が一般式（４）または式（５）で表される化合物を出発物質として製造されたことを特徴とする＜１＞〜＜６＞のいずれかに記載のアゾ顔料の製造方法。

（一般式（４）中、Ｒ_３はアルキル基を表す。）
本発明は上記＜１＞〜＜７＞に記載した事項に関するものであるが参考のためにその他の事項（たとえば下記［１］〜［８］に記載した事項など）についても記載した。 As a result of intensive studies in view of the above-described circumstances, the present inventors have found that the above problems can be achieved by using a heterocyclic amine acid salt having a specific structure as a starting material, and have completed the present invention.
That is, the present invention is as follows.
<1>
A method for producing an azo pigment represented by the general formula (2), comprising the step (a) of obtaining a diazonium compound by mixing an acid salt of an amine represented by the formula (1) and a diazotizing agent. Because
Wherein step (a) is viewed contains the step of adding the diazotization agent in a solution of salt and acid of the amine, the diazotizing agent is nitrosylsulfuric acid, method for producing the azo pigment.

(In General Formula (2), R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, or a 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, acylamino group, aminocarbonylamino group , Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkylsulfinyl group, aryl Sulfinyl 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, Represents an imide group, a phosphoryl group, a sulfo group, a carboxyl group, a phosphono group, or a quaternary ammonium group, G represents a 5- to 6-membered heterocyclic group, and W represents a substituent that can be bonded to the heterocyclic group that G constitutes. Substituents that can be bonded to the heterocyclic group constituting G are a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, and a hydroxyl group. Nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, Siloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group , Arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group Phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, azo group, imide group, phosphoryl group, sulfo group, carboxyl group Represents a syl group, a phosphono group or a quaternary ammonium group. t represents an integer of 0 to 3. )
<2>
The method for producing an azo pigment according to <1>, further comprising a step (b) of mixing and reacting the diazonium compound obtained in the step (a) and a coupling component.
<3>
Furthermore, the manufacturing method of the azo pigment as described in <2> characterized by including the process (c) which adds water to the reaction liquid obtained at the process (b).
<4>
Mixing in the said process (a) is performed at 20 to 50 degreeC, The manufacturing method of the azo pigment in any one of <1>-<3> characterized by the above-mentioned.
<5>
The method for producing an azo pigment according to any one of <1> to <4>, wherein the azo pigment is an azo pigment represented by the following formula (3).

<6>
The method for producing an azo pigment according to any one of <1> to <5>, wherein the acid salt is a sulfate.
<7>
The method for producing an azo pigment according to any one of <1> to <6>, wherein the acid salt is produced using a compound represented by formula (4) or formula (5) as a starting material.

(In general formula (4), R ₃ represents an alkyl group.)
The present invention relates to the items described in <1> to <7> above, but other items (for example, items described in [1] to [8] below) are also described for reference.

（一般式（２）中、Ｒ_１、Ｒ_２は、それぞれ独立に、水素原子又は置換基を表す。Ｇは５〜６員ヘテロ環基を表す。Ｗは、Ｇが構成するヘテロ環基に結合可能な置換基を表す。ｔは０〜３の整数を表す。）
［２］
さらに、前記工程（ａ）で得たジアゾニウム化合物とカップリング成分とを混合して反応させる工程（ｂ）を含むことを特徴とする請求項１記載のアゾ顔料の製造方法。
［３］
さらに、工程（ｂ）で得た反応液に水を加える工程（ｃ）を含むことを特徴とする上記［２］に記載のアゾ顔料の製造方法。
［４］
前記工程（ａ）における混合が２０℃〜５０℃で行われることを特徴とする上記［１］〜［３］のいずれか１項に記載のアゾ顔料の製造方法。
［５］
前記アゾ顔料が下記式（３）で表されるアゾ顔料であることを特徴とする上記［１］〜［４］のいずれか１項に記載のアゾ顔料の製造方法。

［６］
前記酸塩が硫酸塩であることを特徴とする上記［１］〜［５］のいずれか１項に記載のアゾ顔料の製造方法。
［７］
前記酸塩が一般式（４）又は式（５）で表される化合物を出発物質として製造されたことを特徴とする上記［１］〜［６］のいずれか１項に記載のアゾ顔料の製造方法。

（一般式（４）中、Ｒ_３はアルキル基を表す。）
［８］
上記［１］〜［７］のいずれか１項に記載の製造方法で製造されたことを特徴とするアゾ顔料。 [1]
A method for producing an azo pigment represented by the general formula (2), comprising the step (a) of obtaining a diazonium compound by mixing an acid salt of an amine represented by the formula (1) and a diazotizing agent. .

(In General Formula (2), R ₁ and R ₂ each independently represent a hydrogen atom or a substituent. G represents a 5- to 6-membered heterocyclic group. W represents a heterocyclic group that G constitutes. Represents a bondable substituent, and t represents an integer of 0 to 3.)
[2]
The method for producing an azo pigment according to claim 1, further comprising a step (b) of mixing and reacting the diazonium compound obtained in the step (a) with a coupling component.
[3]
The method for producing an azo pigment according to the above [2], further comprising a step (c) of adding water to the reaction solution obtained in the step (b).
[4]
Mixing in the said process (a) is performed at 20 to 50 degreeC, The manufacturing method of the azo pigment of any one of said [1]-[3] characterized by the above-mentioned.
[5]
The said azo pigment is an azo pigment represented by following formula (3), The manufacturing method of the azo pigment of any one of said [1]-[4] characterized by the above-mentioned.

[6]
The method for producing an azo pigment according to any one of the above [1] to [5], wherein the acid salt is a sulfate.
[7]
The azo pigment according to any one of [1] to [6] above, wherein the acid salt is produced using a compound represented by the general formula (4) or the formula (5) as a starting material. Production method.

(In general formula (4), R ₃ represents an alkyl group.)
[8]
An azo pigment produced by the production method according to any one of [1] to [7] above.

  According to the present invention, by using an acid salt of a heterocyclic amine having a specific structure as a starting material, an azo pigment can be produced with high efficiency (purity and productivity) and low cost. A production method and an azo pigment obtained by the method can be provided.

  The process for producing an azo pigment represented by the general formula (2) of the present invention uses an amine acid salt represented by the formula (1) as a starting material, and the amine acid represented by the formula (1). A step (a) of obtaining a diazonium compound by mixing a salt and a diazotizing agent; Moreover, this invention relates also to the azo pigment represented by General formula (2) manufactured with the manufacturing method of the azo pigment of this invention explained in full detail below.

（一般式（２）中、Ｒ_１、Ｒ_２は、それぞれ独立に、水素原子又は置換基を表す。Ｇは５〜６員ヘテロ環基を表す。Ｗは、Ｇが構成するヘテロ環基に結合可能な置換基を表す。ｔは０〜３の整数を表す。）

(In General Formula (2), R ₁ and R ₂ each independently represent a hydrogen atom or a substituent. G represents a 5- to 6-membered heterocyclic group. W represents a heterocyclic group that G constitutes. Represents a bondable substituent, and t represents an integer of 0 to 3.)

1. Production Step As described above, the method includes the step (a) of obtaining a diazonium compound by mixing an acid salt of an amine represented by the formula (1) and a diazotizing agent. Amine acid salts are less soluble in the medium used in step (a) than free amines. For this reason, when an amine acid salt is used, the diazotization reaction during production is moderated and the reaction temperature can be easily controlled. As a result, the purity of the pigment to be synthesized is increased, and the effect of improving filterability and sedimentation can be obtained.
The production method of the present invention preferably includes a step (b) of obtaining a reaction liquid obtained by mixing and reacting the diazonium compound obtained in the step (a) and a coupling component.
More preferably, the production method of the present invention includes a step (c) of adding water to the reaction solution obtained in the step (b). By adding water to the reaction solution, the azo pigment produced in the reaction solution can be taken out in a short time and with a high yield. This is presumably because the azo pigment produced aggregates to form coarse particles by adding water.

Details of the step (a) will be described.
In the step (a), a diazonium compound is derived by a reaction between the acid salt of the amine and the diazotizing agent by mixing the diazotizing agent and the acid salt of the amine represented by the formula (1). This reaction is preferably carried out in a medium containing an acid. In this specification, a liquid containing the diazonium compound is referred to as a “diazonium compound preparation liquid”. The method of mixing the amine acid salt, acid and diazotizing agent is not particularly limited, but it is preferable to add the diazotizing agent to the amine acid salt and acid solution. The diazotizing agent in the step (a) is used to derive an acid salt of an amine into a diazonium compound, and is not limited as long as it has such an action. Representative examples of the diazotizing agent include nitrites (for example, sodium nitrite and potassium nitrite), isoamyl nitrite, and nitrosylsulfuric acid, and more preferably sodium nitrite, potassium nitrite, and nitrosylsulfuric acid. Of these, nitrosylsulfuric acid is particularly preferred.

  The acid used in the step (a) means an acid that can be dissolved even slightly even if the acid salt of the amine is not completely dissolved. As the acid, an inorganic acid and an organic acid can be used. Examples of the inorganic acid include hydrochloric acid, phosphoric acid, and sulfuric acid, preferably phosphoric acid and sulfuric acid, and more preferably sulfuric acid. Examples of the organic acid include formic acid, acetic acid, propionic acid, and methanesulfonic acid, preferably acetic acid, propionic acid, and methanesulfonic acid, and more preferably acetic acid and propionic acid. These acids may be used alone or in combination. Examples of the mixed acid include phosphoric acid / acetic acid, sulfuric acid / acetic acid, methanesulfonic acid / acetic acid, acetic acid / propionic acid, and preferably phosphoric acid / acetic acid, sulfuric acid / acetic acid, sulfuric acid / acetic acid / propionic acid, acetic acid. / Propionic acid, among which sulfuric acid / acetic acid and acetic acid / propionic acid are particularly preferable. 1 / (0.1-20) is preferable, as for the mass ratio of these mixed acids, 1 / (0.5-10) is more preferable, More preferably, it is 1 / (1-10).

In the step (a), the amount of acid added to the acid salt of the amine is preferably 1 to 100 times, more preferably 2 to 50 times, and further preferably 3 to 25 times in terms of mass ratio. When the mass ratio is 1 or more, the stirring property is good and it is advantageous for the induction of the diazonium compound. Further, from the viewpoint of productivity, the mass ratio is preferably 100 times or less.
In addition, the amount of the diazotizing agent added to the amine acid salt in the step (a) is preferably 1.0 to 20 times, more preferably 1.0 to 10 times in terms of molar ratio, and 1.0 More preferably, 5 times. If it is 1.0 times or more, induction to a diazonium compound is easy, and if it is 20 times or less, it is possible to prevent the diazonium compound from being decomposed by a side reaction.

  The mixing of the diazotizing agent and amine acid salt in step (a) is preferably carried out at 50 ° C. or lower, more preferably carried out at 40 ° C. or lower, and further carried out at 30 ° C. or lower. preferable. Further, it is preferably carried out at −10 ° C. or higher, more preferably carried out at 0 ° C. or higher, further preferably carried out at 15 ° C. or higher from the viewpoint of purity and sedimentation, and carried out at 20 ° C. or higher. It is particularly preferred that A temperature of 50 ° C. or lower is preferable from the viewpoint of preventing decomposition of the diazotizing agent in the preparation of the diazo liquid and the diazonium compound generated as a result of the reaction. By setting the temperature to −10 ° C. or higher, the dissolution rate of the acid salt of the amine in the acid can be kept high, and induction into the diazonium compound can be performed in a short time. Moreover, the cost required for temperature management can be reduced. From the above-mentioned various viewpoints, it is preferably carried out at 20 to 50 ° C., particularly preferably carried out at 25 to 30 ° C. The stirring time for inducing the diazonium compound is preferably 0.3 to 10 hours, more preferably 0.5 to 5 hours, and further preferably 1 to 3 hours. By setting the time within this range, the reaction can be carried out completely and the diazonium compound can be prevented from being decomposed.

  As described above, the diazonium compound produced in step (a) is a compound that is unstable particularly at high temperatures. On the other hand, since the reaction between the diazotizing agent and the amine is an exothermic reaction, it is very important to control the mixing temperature in order to proceed the desired reaction with high efficiency. The acid salt of the compound represented by formula (1) in the present invention has low solubility in the medium used in step (a). Therefore, when the acid salt is used as a starting material, the reaction between the diazotizing agent and the amine proceeds gently, so that temperature control is facilitated, and as a result, generation of impurities and decomposition products can be suppressed. This is presumed to contribute to manufacturing efficiency.

  A normal stirrer is used for mixing, and there is no particular limitation. Although depending on the production equipment, the rotation speed of the preferable stirring is preferably 30 to 300 rpm, more preferably 40 to 200 rpm, and still more preferably 50 to 200 rpm. When the stirring speed is 30 rpm or more, the stirring efficiency of the diazonium compound preparation liquid is good, which is preferable for the progress of the reaction.

  The solvent that can be mixed in the step (a) is not particularly limited as long as the derived diazonium compound is not decomposed. Examples of miscible solvents include hydrocarbon solvents such as hexane, benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, ketone solvents such as acetone and methyl ethyl ketone, dimethylformamide, dimethylacetamide, pyrrolidone and N-methyl- Examples include amide solvents such as 2-pyrrolidone, other dimethyl sulfoxide, sulfolane, acetonitrile, and water.

  The preferred pH of the diazonium compound preparation solution in step (a) is preferably 7 or less, more preferably 5 or less, and even more preferably 3 or less. When the pH of the diazonium compound preparation liquid in the step (a) is 7 or less, it is preferable for preventing decomposition of the induced diazonium compound.

Next, details of the step (b) will be described.
In the step (b), the diazonium compound adjusting solution obtained in the step (a) and the coupling component are mixed to couple the diazonium compound and the coupling component in the diazonium compound adjusting solution obtained in the step (a). This is a step of ringing. The method for mixing the diazonium compound adjusting solution obtained in step (a) and the coupling component is not particularly limited, but the diazonium compound adjusting solution obtained in step (a) is mixed in the mixture of the coupling component and solvent. It is preferable to add or add a coupling component to the diazonium compound preparation liquid obtained in the step (a).

  The amount of the diazonium compound in the diazonium compound preparation liquid obtained in the step (a) with respect to the coupling component in the step (b) is preferably 0.8 to 3 equivalents, more preferably the coupling position of the coupling component. It is 0.9-2 equivalent with respect to a coupling position, More preferably, it is 0.95-1.5 equivalent with respect to a coupling position. If it is 0.8 equivalent or less, a coupling component having an unreacted coupling position hardly remains, and if it is 3 equivalents or more, a large amount of unreacted diazonium compound may remain. None of these are economically advantageous.

  In the step (b), a coupling component may be added without using a solvent, or may be added by mixing with a solvent. When using a solvent for the coupling component in the step (b), the solvent is not particularly limited, and examples thereof include alcohol solvents and organic acid solvents. Moreover, the mixed solvent containing an alcohol solvent and the mixed solvent containing an organic acid can also be used. Examples of the alcohol solvent include methanol, ethanol, isopropanol, pentanol, heptanol, octanol, cyclohexanol, benzyl alcohol, phenethyl alcohol, phenylpropyl alcohol, furfuryl alcohol, and anise alcohol. Also not only mono-, but also oligo- (especially di- and tri-) and poly-C2-C4-alkylene glycols (in short "glycols") and their mono-C1-C8-alkyl- and monoaryl ethers ( In short, “glycol monoether”) is also suitable. Also advantageous are compounds based on ethylene. Examples include ethylene glycol, 1,2- and 1,3-propylene glycol, diethylene glycol, butylene glycol, di-, tri- and tetraethylene glycol, di-, tri- and tetrapropylene glycol, polyethylene- and polypropylene glycol, ethylene Glycol monomethyl-, -monoethyl-, -monopropyl-, -monobutyl- and -monohexyl ether and propylene glycol monomethyl-, -monoethyl-, -monopropyl-, -monobutyl- and -monohexyl ether, di-, tri- And tetraethylene glycol monomethyl-, -monoethyl- and -monobutyl ether and di-, tri- and tetrapropylene glycol monomethyl-, -monoethyl- and -monobutyl ether and ethyl - and it includes propylene glycol monophenyl ether. Most preferably, methanol, ethanol, isopropanol, ethylene glycol, diethylene glycol is used. These mixed solvents are also advantageous.

  The amount of the solvent preferably added to the coupling component is preferably 0.5 to 200 times, more preferably 1 to 100 times, and still more preferably 1 to 50 times in terms of mass ratio. If the amount of the solvent preferably added to the coupling component is 0.5 times or more in terms of mass ratio, the coupling component and the solvent can be easily stirred in the production machine, and the desired reaction can proceed. Moreover, it is preferable to set it as 200 times or less from an economical viewpoint.

  Examples of organic acids include formic acid, acetic acid, propionic acid, butyric acid, and methanesulfonic acid, preferably acetic acid, propionic acid, and methanesulfonic acid, and more preferably acetic acid and propionic acid.

  Mixed solvents including alcohol solvents include acetonitrile, formamide, N, N-dimethylformamide, N, N-dimethylacetamide, dimethyl sulfoxide, sulfolane, propylene carbonate, N-methyl-2-pyrrolidone, and N-vinyl-2-pyrrolidone. , N, N-diethyldodecanamide). A mixed solvent of the organic acid and alcohol solvent shown above is also suitable.

Further, the mixture of the coupling component and the solvent may contain a base. Examples of the base include triethylamine, tributylamine, diisopropylethylamine, pyridine, dimethylaminopyridine, DBU (1,8-diazabicyclo [5.4.0] -7-
Examples include organic bases such as undecene and inorganic bases such as lithium carbonate, sodium carbonate, potassium carbonate, sodium hydrogen carbonate, lithium hydroxide, sodium hydroxide, potassium hydroxide. Other examples of salts of organic acids and strong bases include lithium acetate, potassium acetate, sodium oxalate, and disodium ethylenediaminetetraacetate.
When adding a base, the addition time of a base is not specifically limited. The diazonium compound adjusting solution in step (a) may be mixed with the mixed solution of the coupling component, base and solvent, and the diazonium compound adjusting solution and base in step (a) are alternately mixed into the mixed solution of the coupling component and solvent. May be mixed.

  The preferred pH of the mixed solution in the step (b) is preferably 12 or less, more preferably 10 or less, and still more preferably 9 or less. If the pH of the mixed solution in the step (b) is 12 or less, it is preferable for preventing the diazonium compound derived in the step (a) from being decomposed and causing a desired reaction to proceed.

  In the step (b), the mixing temperature of the diazonium compound preparation liquid and the coupling component in the step (a) is preferably 50 ° C. or lower, more preferably 30 ° C. or lower, still more preferably 25 ° C. It is desirable to carry out the following. If it is 50 degrees C or less, decomposition | disassembly of the azo pigment represented by the diazonium compound induced | guided | derived at the process (a) and the produced | generated general formula (2) can be prevented. Moreover, a normal stirrer is used for mixing, and there is no limitation in particular. Although depending on the production equipment, the rotation speed of the preferable stirring is preferably 30 to 300 rpm, more preferably 40 to 200 rpm, and still more preferably 50 to 200 rpm. If the stirring speed is within this range in terms of the number of revolutions, the stirring efficiency of the mixed solution is good, which is preferable for allowing the desired reaction to proceed. The stirring time in the step (b) is preferably from 0.1 to 10 hours, more preferably from 0.3 to 5 hours, still more preferably from 0.3 to 3 hours. If it is 0.1 hour or longer, it can be completely induced to the pigment, and if it is 10 hours or shorter, it is preferable for preventing the decomposition of the azo pigment represented by the general formula (2).

  In the mixing of the diazonium compound preparation solution and the coupling component in step (a) in step (b), two or more compounds may be used as the diazonium compound and / or coupling component in the diazonium compound preparation solution. In this case, two or more kinds of azo pigments represented by the general formula (2) to be obtained are produced at the same time.

  The coupling component used in the step (b) is preferably a compound represented by the following general formula (6).

(In General Formula (6), R ₁ and R ₂ each independently represent a hydrogen atom or a substituent. G represents a 5- to 6-membered heterocyclic group. W represents a heterocyclic group that G constitutes. Represents a bondable substituent, and t represents an integer of 0 to 3.)

_G, examples of the substituents of R 1, _{R 2} and W are, _G in the general formula (2) described below _are the same as the examples of R 1, _{R 2} and W, and preferred examples thereof are also the same.

P ₁ and P ₂ represent a hydrogen atom or a leaving group. The leaving group means a group that is eliminated by a chemical reaction, for example, a group that is eliminated by a coupling reaction with a diazonium compound, or a group that easily causes an addition elimination reaction with an oxidized form of a phenylenediamine derivative. P ₁ and P ₂ are preferably a hydrogen atom, a halogen atom, an alkyloxy group, an aryloxy group, an alkylthio group, or an arylthio group, more preferably a hydrogen atom or a halogen atom, and most preferably a hydrogen atom.

Next, details of the step (c) will be described.
Step (c) is a step of adding water to the reaction solution obtained in step (b).
The amount of water to be added is preferably 0.5 to 50 times, more preferably 1 to 20 times, and still more preferably 1 to 10 times the mass ratio of the coupling component. Moreover, it is preferable that a stirrer is used at the time of addition. As the stirrer, a normal one is used and is not particularly limited. Although depending on the production equipment, the rotation speed of the preferable stirring is preferably 30 to 300 rpm, more preferably 40 to 200 rpm, and still more preferably 50 to 200 rpm.

In the method for producing an azo pigment of the present invention, the product obtained by the above steps (a) to (c) is treated according to a normal post-treatment method of an organic synthesis reaction and then purified or used without purification. Can do.
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 azo pigment represented by the general formula (2) produced by the method of the present invention may be post-treated as necessary. 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.

2. Azo Pigment The azo pigment produced by the method for producing an azo pigment of the present invention is represented by the following general formula (2).
Hereinafter, the azo pigment represented by the general formula (2) in the present invention will be described in detail. The azo pigment may be a salt or hydrate thereof.

(In General Formula (2), R ₁ and R ₂ each independently represent a hydrogen atom or a substituent. G represents a 5- to 6-membered heterocyclic group. W represents a heterocyclic group that G constitutes. Represents a bondable substituent, and t represents an integer of 0 to 3.)

Hereinafter, R ₁ , R ₂ , G, W, and t will be described in more detail.
R ₁ and R ₂ each independently represents a hydrogen atom or a substituent.
Examples of substituents for R ₁ and R ₂ are each independently a halogen atom, alkyl group, cycloalkyl 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, arylsulfonylamino group, alkylthio group, arylthio group, heterocycle O 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, phosphine group Examples thereof include a finylamino group, a silyl group, an azo group, an imide group, a phosphoryl group, or an ionic hydrophilic group, each of which may further have a substituent.

Among these, particularly preferred R ₁ and R 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, aryl A sulfonylamino group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, or an alkoxycarbonyl group, particularly a hydrogen atom, halogen atom, alkyl group, aryl group, cyano group, hydroxyl group, alkylsulfonyl group, arylsulfonyl Group, heterocyclic group or alkoxycarbonyl group is preferred, and a hydrogen atom, alkyl group, aryl group, hydroxyl group or alkoxycarbonyl group is most preferred.
R ₁ and R ₂ are more preferably a methyl group, an i-propyl group, or a t-butyl group.

Hereinafter, R ₁ and R ₂ will be described in more detail.
The halogen atom represented by R ₁ and R ₂ 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 and R ₂ includes a substituted or unsubstituted alkyl group. The substituted or unsubstituted alkyl group is preferably an alkyl group having 1 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent quoted by R < ₁ > and R < ₂ > in the said General formula (2) can be mentioned. Of these, a hydroxy group, an alkoxy group, a cyano group, a halogen atom, a sulfo group (may be in the form of a salt) or a carboxyl group (may be in the form of a salt) is preferable. Examples of the alkyl group include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, s-butyl group, t-butyl group, n-octyl group, and eicosyl. Group, 2-chloroethyl group, hydroxyethyl group, cyanoethyl group or 4-sulfobutyl group.

The cycloalkyl group represented by R ₁ and R ₂ includes a substituted or unsubstituted cycloalkyl group. The substituted or unsubstituted cycloalkyl group is preferably a cycloalkyl group having 5 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent quoted by R < ₁ > and R < ₂ > in the said General formula (2) can be mentioned. Examples of the cycloalkyl group may include cyclohexyl, cyclopentyl, or 4-n-dodecylcyclohexyl.

The aralkyl group represented by R ₁ and R ₂ 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. As an example of a substituent, the same thing as the substituent quoted by R < ₁ > and R < ₂ > in the said General formula (2) can be mentioned. Examples of the aralkyl include benzyl and 2-phenethyl.

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

The aryl group represented by R ₁ and R ₂ is a substituted or unsubstituted aryl group having 6 to 30 carbon atoms, such as phenyl, p-tolyl, naphthyl, m-chlorophenyl, or o-hexadecanoylaminophenyl. . As an example of a substituent, the same thing as the substituent quoted by R < ₁ > and R < ₂ > in the said General formula (2) can be mentioned.

The heterocyclic group represented by R ₁ and R ₂ is a monovalent group obtained by removing one hydrogen atom from a 5- or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic group compound. , They may be further condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent quoted by R < ₁ > and R < ₂ > in the said General formula (2) can be mentioned. Examples of the heterocyclic group include, but are not limited to, substitution positions: pyridine ring, pyrazine ring, pyridazine ring, pyrimidine ring, triazine ring, quinoline ring, isoquinoline ring, quinazoline ring, cinnoline ring, phthalazine ring, quinoxaline ring , Pyrrole ring, indole ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrazole ring, imidazole ring, benzimidazole ring, triazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole ring, isothiazole ring Benzoisothiazole ring, thiadiazole ring, isoxazole ring, benzisoxazole ring, pyrrolidine ring, piperidine ring, piperazine ring, imidazole ring, thiazole ring and the like.

The alkoxy group represented by R ₁ and R ₂ 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. As an example of a substituent, the same thing as the substituent quoted by R < ₁ > and R < ₂ > in the said General formula (2) can be mentioned. Examples of the alkoxy group include methoxy, ethoxy, isopropoxy, n-octyloxy, methoxyethoxy, hydroxyethoxy and 3-carboxypropoxy.

The aryloxy group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted aryloxy group having 6 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent quoted by R < ₁ > and R < ₂ > in the said General formula (2) can be mentioned. 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 and R ₂ is preferably a silyloxy group having 3 to 20 carbon atoms, and examples thereof include trimethylsilyloxy and t-butyldimethylsilyloxy.

The heterocyclic oxy group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted heterocyclic oxy group having 2 to 30 carbon atoms. As an example of a substituent, the same thing as the substituent quoted by R < ₁ > and R < ₂ > in the said General formula (2) can be mentioned. Examples of the heterocyclic oxy group include 1-phenyltetrazol-5-oxy, 2-tetrahydropyranyloxy and the like.

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

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

The aryloxycarbonyloxy group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted aryloxycarbonyloxy group having 7 to 30 carbon atoms. Examples of the substituent include R in the general formula (2). It includes the same as the substituents exemplified in ₁ and R _2. Examples of the aryloxycarbonyloxy group include phenoxycarbonyloxy, p-methoxyphenoxycarbonyloxy, pn-hexadecyloxyphenoxycarbonyloxy and the like.

The amino group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted alkylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylamino group having 6 to 30 carbon atoms. Can be the same as the substituents mentioned for R ₁ and R ₂ in the general formula (2). 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 and R ₂ is preferably a formylamino group, a substituted or unsubstituted alkylcarbonylamino group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylcarbonylamino group having 6 to 30 carbon atoms. Examples of the substituent include the same substituents as those described for R ₁ and R ₂ in the general formula (2). Examples of the acylamino group include formylamino, acetylamino, pivaloylamino, lauroylamino, benzoylamino, 3,4,5-tri-n-octyloxyphenylcarbonylamino, and the like.

The aminocarbonylamino group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted aminocarbonylamino group having 1 to 30 carbon atoms. Examples of the substituent include R ₁ in the general formula (2) and It includes the same as the substituents exemplified in R _2. Examples of the aminocarbonylamino group include carbamoylamino, N, N-dimethylaminocarbonylamino, N, N-diethylaminocarbonylamino, morpholinocarbonylamino and the like.

The alkoxycarbonylamino group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted alkoxycarbonylamino group having 2 to 30 carbon atoms. Examples of the substituent include R ₁ and R in the general formula (2). _The same substituents as mentioned in ₂ can be mentioned. 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 and R ₂ is preferably a substituted or unsubstituted aryloxycarbonylamino group having 7 to 30 carbon atoms, and examples of the substituent include R in the general formula (2). It includes the same as the substituents exemplified in ₁ and R _2. Examples of the aryloxycarbonylamino group include phenoxycarbonylamino, p-chlorophenoxycarbonylamino, mn-octyloxyphenoxycarbonylamino and the like.

The sulfamoylamino group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted sulfamoylamino group having 0 to 30 carbon atoms, and examples of the substituent include R in the general formula (2). It includes the same as the substituents exemplified in ₁ and R _2. Examples of the sulfamoylamino group include sulfamoylamino, N, N-dimethylaminosulfonylamino, Nn-octylaminosulfonylamino and the like.

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

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

The arylthio group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted arylthio group having 6 to 30 carbon atoms, and examples of the substituent include those described for R ₁ and R ₂ in the general formula (2). The same thing as a substituent can be mentioned. Examples of the arylthio group include phenylthio, p-chlorophenylthio, m-methoxyphenylthio and the like.

The heterocyclic thio group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted heterocyclic thio group having 2 to 30 carbon atoms. Examples of the substituent include R ₁ in the general formula (2) and It includes the same as the substituents exemplified in R _2. Examples of the heterocyclic thio group include 2-benzothiazolinylthio, 1-phenyltetrazolinyl-5-ylthio and the like.

The sulfamoyl group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted sulfamoyl group having 0 to 30 carbon atoms. Examples of the substituent include R ₁ and R ₂ in the general formula (2). And the same substituents as those described above. 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 alkylsulfinyl group and arylsulfinyl group represented by R ₁ and R ₂ are preferably a substituted or unsubstituted alkylsulfinyl group having 1 to 30 carbon atoms or a substituted or unsubstituted arylsulfinyl group having 6 to 30 carbon atoms. Examples of the same can be the same as the substituents mentioned for R ₁ and R ₂ in the general formula (2). Examples of the alkyl and arylsulfinyl groups include methylsulfinyl, ethylsulfinyl, phenylsulfinyl, p-methylphenylsulfinyl and the like.

The alkylsulfonyl group and arylsulfonyl group represented by R ₁ and R ₂ are preferably a substituted or unsubstituted alkylsulfonyl group having 1 to 30 carbon atoms, or a substituted or unsubstituted arylsulfonyl group having 6 to 30 carbon atoms. Examples of the same can be the same as the substituents mentioned for R ₁ and R ₂ in the general formula (2). Examples of the alkyl and arylsulfonyl groups include methylsulfonyl, ethylsulfonyl, phenylsulfonyl, p-toluenesulfonyl and the like.

The acyl group represented by R ₁ and R ₂ is a formyl group, a substituted or unsubstituted alkylcarbonyl group having 2 to 30 carbon atoms, a substituted or unsubstituted arylcarbonyl group having 7 to 30 carbon atoms, or a group having 4 carbon atoms. A heterocyclic carbonyl group bonded to a carbonyl group with 30 substituted or unsubstituted carbon atoms is preferable, and examples of the substituent are the same as those described for R ₁ and R ₂ in the general formula (2). Things can be mentioned. Examples of the acyl group include acetyl, pivaloyl, 2-chloroacetyl, stearoyl, benzoyl, pn-octyloxyphenylcarbonyl, 2-pyridylcarbonyl, 2-furylcarbonyl and the like.

The aryloxycarbonyl group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted aryloxycarbonyl group having 7 to 30 carbon atoms, and examples of the substituent include R ₁ and R ₁ in the general formula (2). It includes the same as the substituents exemplified in R _2. Examples of the aryloxycarbonyl group include phenoxycarbonyl, o-chlorophenoxycarbonyl, m-nitrophenoxycarbonyl, pt-butylphenoxycarbonyl, and the like.

The alkoxycarbonyl group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted alkoxycarbonyl group having 2 to 30 carbon atoms. Examples of the substituent include R ₁ and R ₂ in the general formula (2). The same thing as the substituent mentioned can be mentioned. Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, t-butoxycarbonyl, n-octadecyloxycarbonyl and the like.

The carbamoyl group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted carbamoyl group having 1 to 30 carbon atoms. Examples of the substituent include R ₁ and R ₂ in the general formula (2). And the same substituents as those described above. 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 and R ₂ is preferably a substituted or unsubstituted phosphino group having 2 to 30 carbon atoms, and examples of the substituent include R ₁ and R ₂ in the general formula (2). And the same substituents as those described above. Examples of the phosphino group include dimethylphosphino, diphenylphosphino, methylphenoxyphosphino and the like.

The phosphinyl group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted phosphinyl group having 2 to 30 carbon atoms, and examples of the substituent include R ₁ and R ₂ in the general formula (2). And the same substituents as those described above. Examples of the phosphinyl group include phosphinyl, dioctyloxyphosphinyl, diethoxyphosphinyl and the like.

The phosphinyloxy group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted phosphinyloxy group having 2 to 30 carbon atoms. Examples of the substituent include R in the general formula (2). It includes the same as the substituents exemplified in ₁ and R _2. Examples of the phosphinyloxy group include diphenoxyphosphinyloxy and dioctyloxyphosphinyloxy.

The phosphinylamino group represented by R ₁ and R ₂ is preferably a substituted or unsubstituted phosphinylamino group having 2 to 30 carbon atoms, and examples of the substituent include R in the general formula (2). It includes the same as the substituents exemplified in ₁ and R _2. Examples of the phosphinylamino group include dimethoxyphosphinylamino and dimethylaminophosphinylamino.

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

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

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

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

Examples of the ionic hydrophilic group represented by R ₁ and R ₂ 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).

  In the general formula (2), preferred examples of the 5- to 6-membered heterocyclic group constituted by G are preferably 5-membered or 6-membered substituted or unsubstituted aromatic or non-aromatic heterocyclic groups, Further, it may be condensed. More preferably, it is a 5- or 6-membered aromatic heterocyclic group having 3 to 30 carbon atoms.

  Examples of the heterocyclic group represented by G include a pyridine ring, a pyrazine ring, a pyridazine ring, a pyrimidine ring, a triazine ring, a quinoline ring, an isoquinoline ring, a quinazoline ring, a cinnoline ring; Phthalazine ring, quinoxaline ring, pyrrole ring, indole ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, pyrazole ring, imidazole ring, benzimidazole ring, triazole ring, oxazole ring, benzoxazole ring, thiazole ring, benzothiazole Ring, isothiazole ring, benzisothiazole ring, thiadiazole ring, isoxazole ring, benzisoxazole ring, pyrrolidine ring, piperidine ring, piperazine ring, imidazoline ring, thiazoline ring, sulfolane ring and the like.

  Furthermore, a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring are preferable, and among them, a pyridine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring are preferable, and a pyridine ring, a pyrimidine ring, and a triazine ring are more preferable.

When multiple W exists, it represents a substituent each independently.
Examples of the substituents of W are the same as examples of R ₁ and R ₂ in the general formula (2).
Among these, particularly preferred W is independently a halogen atom, alkyl group, alkoxy group, aryl group, heterocyclic group, cyano group, hydroxyl group, alkoxy group, amino group, amide group, ureido group, alkylsulfonylamino group, aryl. A sulfonylamino group, a sulfamoyl group, an alkylsulfonyl group, an arylsulfonyl group, a carbamoyl group, or an alkoxycarbonyl group, particularly a hydrogen atom, a halogen atom, an alkyl group, an alkoxy group, an aryl group, a cyano group, a hydroxyl group, an amino group, An alkylsulfonyl group, an arylsulfonyl group, a heterocyclic group, or an alkoxycarbonyl group is preferable, and an alkyl group, an alkoxy group, an aryl group, a hydroxyl group, an amino group, and an alkoxycarbonyl group are more preferable, an alkoxy group, a hydroxy group Group, an amino group is most preferred.

  In general formula (2), t represents an integer of 0 to 3, preferably 0 to 2, more preferably 1 or 2, and most preferably 1.

  In the present invention, the preferred combination of substituents of the azo compound represented by the general formula (2) and the azo pigment is preferably a compound in which at least one of the various substituents is the above-mentioned preferred group. A compound in which the substituent is the preferred group is more preferable, and a compound in which all the substituents are the preferred group is most preferable.

  In the present invention, particularly preferred combinations as the azo compound and the azo pigment represented by the general formula (2) include the following (a) to (d).

(I) G is preferably a 5- to 6-membered nitrogen-containing heterocyclic group, particularly preferably an s-triazine ring, pyrimidine ring, pyridazine ring, pyrazine ring, pyridine ring, imidazole ring, pyrazole ring, thiadiazole ring or pyrrole ring, Among them, s-triazine ring, pyridine ring, pyrimidine ring, thiadiazole ring or pyridazine ring is preferable, and 4,6-pyrimidine ring and s-triazine ring are most preferable.

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

(C) 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 An alkylthio group, a substituted or unsubstituted arylthio group, and a carbonyl group (—CO—) are preferable. In particular, a hydroxyl group, a substituted or unsubstituted amino group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted alkylthio group, and a carbonyl group. Among them, a hydroxyl group, a methoxy group, an amino group, and a dimethylamino group are more preferable, a hydroxyl group, a methoxy group, and an amino group are more preferable, and a methoxy group is most preferable.

(D) t represents an integer of 0 to 3, preferably 0 to 2, more preferably 0 or 1, and most preferably 1.

  Most preferred as the azo pigment represented by the general formula (2) is an azo pigment represented by the following formula (3).

The azo compound represented by the general formula (2) can take several tautomers in terms of chemical structure, but the pigment having the extreme structural formula represented by the general formula (2) From the viewpoint of dispersibility and dispersion stability when used, it is preferable. A mixture containing a tautomer other than the structure represented by the general formula (2) may be used, but the tautomer content is preferably 30% or less, more preferably 10% or less. Most preferably, it is 0%.
Specific examples (illustrated azo compounds Pig-1 to Pig-8) of the azo compounds represented by the general formula (2) are shown below, but the azo compounds of the present invention are not limited to the following examples. .

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

  In the present invention, when the pigment represented by the general formula (2) has an acid group, a part or all of the acid group may be a salt type, and a salt type pigment and a free acid type may be used. The pigment may be mixed. Examples of the salt type include salts of alkali metals such as Na, Li, and K, ammonium salts that may be substituted with alkyl groups or hydroxyalkyl groups, 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 pigment represented by the general formula (2), 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. . These pigments may be hydrates containing water molecules in the crystals.

  In addition, regarding the pigment represented by the general formula (2), tautomers thereof (for example, azo-hydrazone tautomers) are also included in these general formulas in the present invention.

3. Amine acid salt The amine acid salt used as a starting material in the process for producing an azo pigment of the present invention is represented by the formula (1).

  Examples of acid salts include organic acid salts and inorganic acid salts. Specific examples include acetates, phosphates, hydrochlorides, sulfates, oxalates, methanesulfonates, benzoates or phthalates. Salts are preferred, hydrochlorides, sulfates or oxalates are more preferred, hydrochlorides or sulfates are more preferred, and sulfates are most preferred.

  Examples of the method for producing an amine acid salt represented by the formula (1) include a method of reacting an isolated amine represented by the formula (1) and an acid, the following general formula (4) or the formula ( There is a method of reacting methylhydrazine with the compound represented by 5) as a starting material, and then adding an acid to the reaction mixture. From the economical viewpoint, it is not necessary to take out the intermediate, and the following general formula (4) ) Or a compound represented by formula (5) and methylhydrazine are reacted, and then an acid is added to the reaction mixture.

(In general formula (4), R ₃ represents an alkyl group.)
Examples of preferable R _{3 in} the general formula (4) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, and an n-butyl group, preferably a methyl group and an ethyl group, and most preferably Is an ethyl group.

  1.0-2.0 are preferable, as for the molar equivalent of the methyl hydrazine with respect to the compound represented by General formula (4) or Formula (5), 1.0-1.4 are more preferable, and 1.0-1. 2 is more preferable. When it is less than 1.0, the unreacted intermediate is likely to remain. Moreover, since the unreacted residue of methyl hydrazine is not preferable in terms of environmental protection, safety and economy from the viewpoint of waste liquid treatment, the molar equivalent is preferably closer to 1.0 equivalent.

As the solvent, those capable of dissolving methyl hydrazine and the compound represented by formula (4) or formula (5) are preferable.
For example, water, alcohol (1 to 10 carbon atoms), acetonitrile, acetate (2 to 10 carbon atoms), aromatic hydrocarbon (6 to 20 carbon atoms), dimethyl sulfoxide, sulfolane, dimethylformamide, dimethylacetamide, acetone, methyl ethyl ketone , N-methylpyrrolidone, diethyl ether, diisopropyl ether and the like. Water, methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, butyl acetate, toluene, o-, m-, p-xylene (or a mixture thereof), dimethyl sulfoxide, dimethylacetamide, acetone, N-methylpyrrolidone are preferred, and water , Methanol, ethanol, isopropanol, acetonitrile, ethyl acetate, toluene, dimethyl sulfoxide, dimethylacetamide, acetone, and N-methylpyrrolidone are more preferable, and water, methanol, isopropanol, acetone, ethyl acetate, and toluene are still more preferable. Moreover, you may use the mixed solvent which mixed these by arbitrary 2 or more types of combinations and composition ratios.

The reaction temperature is preferably 0 ° C to 200 ° C, more preferably 30 ° C to 150 ° C, and still more preferably 40 ° C to 80 ° C.
The reaction time is preferably 5 minutes to 8 hours, more preferably 15 minutes to 5 hours, and even more preferably 30 minutes to 3 hours.

When the starting material is a compound represented by the formula (5), the reaction is preferably performed under a nitrogen stream. This is because ammonia produced as a by-product is removed from the reaction system, thereby promoting the reaction and suppressing the side reaction. It is also preferable to carry out under heating and reflux because the same effect as that obtained under the above-described nitrogen stream is obtained. Furthermore, a better effect can be obtained by carrying out under a nitrogen stream and heating under reflux.
In the above operation, other gases such as argon and air can be used in the same manner instead of nitrogen. Further, these gases may be bubbled.

  In addition, it is preferable to add a compound such as an acid anhydride, an acid chloride, an aldehyde, a ketone, or an ester after the reaction is completed in order to remove excess raw materials and by-products. The compound to be added is preferably acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, acetone, methyl ethyl ketone, acetyl chloride, thionyl chloride, acetaldehyde, etc., and acetic anhydride, phthalic anhydride, succinic anhydride, maleic anhydride, etc. Acetone, acetyl chloride, and thionyl chloride are more preferable, and acetic anhydride, acetone, and acetyl chloride are most preferable. These may be used singly or a plurality of them may be added in order, or a mixture of them in an arbitrary ratio may be used.

  By adding an inorganic acid or an organic acid to the reaction mixture obtained as described above, an acid salt of the compound represented by the formula (1) can be obtained. The pH in the conversion to acid salt is preferably 0 to 4, more preferably 0 to 2, and still more preferably 0 to 1.

  The acid salt of the compound represented by the formula (1) can be used after being treated according to a post-treatment method of a normal organic synthesis reaction and then purified or not purified.

4). Applications Applications of the azo pigments of the present invention obtained by the production method of the present invention include image recording materials for forming images, particularly color images, and specifically, inkjet recording described in detail below. In addition to materials, there are heat-sensitive recording materials, pressure-sensitive recording materials, recording materials using electrophotographic methods, transfer-type silver halide photosensitive materials, printing inks, recording pens, etc., preferably ink-jet recording materials, heat-sensitive recording materials, A recording material using an electrophotographic method, more preferably an ink jet recording material.

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

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.
Examples 6 and 7 shall be read as “reference examples”.

[Synthesis Example 1]
52.0 parts of a compound represented by the following formula (1) was added to 230 parts of isopropanol and heated to 45 ° C. to complete dissolution. To this solution, 36.3 parts of concentrated sulfuric acid was added dropwise over 20 minutes. After completion of the dropping, the reaction solution was cooled to 5 ° C., and the produced powder was separated by filtration. After thoroughly washing with isopropanol, it was dried at 50 ° C. for 3 hours to obtain 84.1 parts (yield 99.1%) of the sulfate of the compound represented by the formula (1).

[Synthesis Example 2]
50.0 parts of the compound represented by the formula (1) was added to 220 parts of isopropanol and heated to 45 ° C. for complete dissolution. To this solution, 27.0 parts of concentrated hydrochloric acid was added dropwise over 20 minutes. After completion of the dropping, the reaction solution was cooled to 5 ° C., and the produced powder was separated by filtration. After thoroughly washing with isopropanol, it was dried at 50 ° C. for 3 hours to obtain 50.0 parts (yield 81.0%) of hydrochloride of the compound represented by the formula (1).

[Synthesis Example 3]
68.5 parts of formamidine acetate and 80.7 parts of methyl cyanoacetate were stirred together with 60 parts of methanol at room temperature. Next, 79.9 parts of triethylamine was added under a nitrogen stream. Thereafter, the mixture was heated to an internal temperature of 65 ° C. and stirred for 3 hours while heating under reflux to obtain a solution containing a compound represented by the following formula (5).
Next, the internal temperature of the reaction solution was cooled to 30 to 40 ° C., and 120 parts of isopropanol was injected. Subsequently, 30.3 parts of methyl hydrazine was added dropwise at the same temperature, heated to an internal temperature of 50 ° C., and stirred for 2 hours. Thereafter, the internal temperature was lowered to 20 ° C., 390 parts of acetone was added dropwise, and the mixture was stirred as it was for 30 minutes. Subsequently, 67.9 parts of acetic anhydride was added dropwise and stirred as it was for 30 minutes. Further, 162 parts of concentrated sulfuric acid was added dropwise at an internal temperature of 20-30 ° C. After stirring at the same temperature for 1 hour, the obtained crystals were filtered off. After thoroughly washing with isopropanol, it was dried at 50 ° C. for 3 hours to obtain 138 parts of a sulfate of the compound represented by the formula (1).

[Synthesis Example 4]
207.3 parts of methyl cyanoacetate and 620.0 parts of triethyl orthoformate were injected at an internal temperature of 20-30 ° C., and the mixture was stirred and mixed. Further, 56.5 parts of glacial acetic acid and 533.9 parts of acetic anhydride were injected at an internal temperature of 20 to 30 ° C., and stirred and mixed.
The mixture was heated under nitrogen bubbling and stirred at 110 ° C. for 4 hours while distilling off volatile components at normal pressure. Then, stirring was further continued until acetic acid and acetic anhydride were distilled off to obtain a compound quantitatively represented by the following formula (4-1).

^{The result of 1} H-NMR identification data (chemical shift value) is as follows.
¹ H-NMR (300 MHz, DMSO-d ₆ ): 8.4 (1H, s), 4.5 (2H, q, OCH ₂ —), 3.7 (3H, s, CO ₂ CH ₃ ), 1 .3 (3H, t, OCH ₂ CH ₃ )
Methylhydrazine (36.4 parts) was stirred together with 51.0 parts of isopropanol at an internal temperature of 20 to 25 ° C. To this solution, a solution prepared by dissolving 100.0 parts of the compound represented by (4-1) in 55.7 parts of isopropanol in advance was added dropwise while maintaining an internal temperature of 20 to 25 ° C. Thereafter, the mixture was stirred for about 15 minutes to stabilize the internal temperature at 20 to 25 ° C. Subsequently, it heated to 45 degreeC of internal temperature, and stirred at 45 degreeC for 60 to 90 minutes. After completion of the reaction, 79.9 parts of concentrated sulfuric acid was added dropwise to the reaction solution at the same temperature, and the mixture was cooled to 10 ° C. or lower and stirred for 60 minutes. The produced crystal was separated by filtration and washed with a mixed solvent of 99.1 parts normal heptane / 19.9 parts isopropanol which had been cooled to 0 to 5 ° C. in advance. It dried at 50 degreeC for 3 hours, and obtained 155.0 parts of sulfates of the compound represented by Formula (1).
^{The result of 1} H-NMR identification data (chemical shift value) is as follows.
¹ H-NMR (300 MHz, CD ₃ OD): 8.0 (1H, s, H), 3.8 (3H, s, OMe), 3.7 (3H, s, NMe)

[Example 1]
In a mixed solvent of 64.8 g of glacial acetic acid and 16.2 g of propionic acid, 26.3 g of the sulfate of the compound represented by the above formula (1) synthesized in Synthesis Example 1 was added and stirred at 200 rpm. At this time, the system was a suspension. The suspension was cooled to 5 ° C., and 34.1 g of nitrosylsulfuric acid (43% by mass sulfuric acid solution) was added dropwise over 5 minutes. During this time, the internal temperature rose to 13 ° C. After completion of dropping, the temperature was raised to 25 ° C. to 30 ° C. and stirred for 1 hour. After completion of the reaction, the mixture was cooled to 25 ° C. or lower, and 2.4 g of urea was added in portions while maintaining the same temperature. The mixture was stirred for 15 minutes to obtain a diazonium compound preparation solution. This diazonium compound preparation solution was dropped at 0 ° C. or less into a solution in which 20.0 g of a compound represented by the following formula (6-1) was suspended in 180.0 g of methanol. After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours to be reacted. After completion of the reaction, 240.0 g of water was added and allowed to stand overnight. The next day, the supernatant was removed by decantation and the same amount of water was added. After adjusting the pH to 6.0 by adding 28% by mass aqueous ammonia, the crystals were filtered off using a 110 mm Nutsche. After washing with a sufficient amount of water, it was dried at 60 ° C. for 7 hours to obtain 35.3 g (yield 94.8%) of (Pig-1).

[Example 2]
In the same manner as in Example 1, the sulfate of the formula (1) synthesized in Synthesis Example 1 was changed to the hydrochloride of the formula (1) synthesized in Synthesis Example 2, and (Pig-1) was changed. Obtained.
[Example 3]

  In the same manner as in Example 1, (Pig-1) was changed from the sulfate of the formula (1) synthesized in Synthesis Example 1 to the sulfate of the formula (1) synthesized in Synthesis Example 3. Obtained.

[Example 4]
The fact that the sulfate of formula (1) synthesized in Synthesis Example 1 was changed to the sulfate of formula (1) synthesized in Synthesis Example 4 was the same as in Example 1, and (Pig-1) was changed. Obtained.
[Example 5]
In a mixed solvent of 64.8 g of glacial acetic acid and 16.2 g of propionic acid, 26.3 g of the sulfate of the compound represented by the above formula (1) synthesized in Synthesis Example 1 was added and stirred at 200 rpm. The suspension was cooled to 5 ° C., and 34.1 g of nitrosylsulfuric acid (43% by mass sulfuric acid solution) was added dropwise over 10 minutes. After completion of dropping, the mixture was stirred for 1 hour at an internal temperature of 10 ° C. After completion of the reaction, 2.4 g of urea was added in portions while maintaining the same temperature. The mixture was stirred for 15 minutes to obtain a diazonium compound preparation solution. Thereafter, in the same manner as in Example 1, it was reacted with 20.0 g of the compound represented by the formula (6-1) to obtain 35.3 g (yield 94.8%) of (Pig-1).

[Comparative Example 1]
Instead of using the sulfate of the above formula (1) synthesized in Synthesis Example 1, the compound free form of the formula (1) was changed to 16.1 g. When the compound free form of the formula (1) was added to a mixed solvent of 64.8 g of glacial acetic acid and 16.2 g of propionic acid, it was completely dissolved. When this solution was cooled to 5 ° C. and 34.1 g of nitrosylsulfuric acid (43% by mass sulfuric acid solution) was added dropwise, the heat generation was intense and the internal temperature rose to 25 ° C. Since dropping was carried out so as to maintain the internal temperature at 25 ° C. or lower, the dropping time required 15 minutes. Thereafter, in the same manner as in Example 1, (Pig-1) was obtained.

[Evaluation]
For Examples 1 to 5 and Comparative Example 1, the purity of the obtained (Pig-1), the amount of solvent that could be decanted, and the filterability were compared. The larger the amount of the solvent that can be decanted, the smaller the required amount of aqueous ammonia necessary for neutralization in the subsequent step, and therefore the less contamination of the inorganic salt produced by neutralization with the pigment is preferred. The results are shown in the table below. In addition, the purity measurement of (Pig-1) was performed using SHIMADZU C-R10A CHROMATAPAC. Regarding filterability, the filtration time was within 1 minute: ◎ longer than 1 minute and 2 minutes or less: ◯ longer than 2 minutes and 3 minutes or less: Δ longer than 3 minutes: x.

[Example 6]
To a mixed solvent of 58.3 g of glacial acetic acid and 22.6 g of concentrated sulfuric acid, 43.3 g of nitrosylsulfuric acid (43% by mass sulfuric acid solution) was added dropwise at 25 ° C. or lower. To this solution, 33.7 g of the sulfate of the above formula (1) synthesized in Synthesis Example 3 was added over 10 minutes while dividing. During this time, the reaction temperature was maintained at 25 ° C. or lower. After completion of the addition, the temperature was raised to 25-30 ° C., and the mixture was stirred at 150 rpm for 1 hour. After completion of the reaction, the mixture was cooled to 25 ° C. or lower, and 2.5 g of urea was added in portions while maintaining the same temperature. The mixture was stirred for 15 minutes to obtain a diazonium compound preparation solution. The diazonium compound preparation solution was dropped into 200 g of methanol that had been cooled to 0 ° C. or lower in advance, and then 35.0 hours while dividing 25.0 parts of the compound represented by the above formula (6-1) at the same temperature. Added over time. After completion of the addition, the reaction was allowed to stir at the same temperature for 2 hours. After completion of the reaction, 175 g of water was added and allowed to stand overnight. The next day, the supernatant was removed by decantation and the same amount of water was added. After adjusting the pH to 6.0 by adding 28% by mass aqueous ammonia, the crystals were filtered off using a 110 mm Nutsche. After washing with a sufficient amount of water, it was dried at 60 ° C. for 7 hours to obtain 45.2 g (yield 97.1%) of (Pig-1).

[Example 7]
To a mixed solvent of 58.3 g of glacial acetic acid and 22.6 g of concentrated sulfuric acid, 43.3 g of nitrosylsulfuric acid (43% by mass sulfuric acid solution) was added dropwise at 25 ° C. or lower. To this solution, 33.7 g of the sulfate of the above formula (1) synthesized in Synthesis Example 3 was added over 10 minutes while dividing. During this time, the reaction temperature was maintained at 25 ° C. or lower. After completion of the addition, the temperature was raised to 25 to 30 ° C. and stirred at 150 rpm for 1 hour to obtain a diazonium compound preparation solution. 2.5 g of urea was dissolved in 300 g of methanol that had been cooled to 0 ° C. or lower in advance, and the diazonium compound preparation solution was added dropwise thereto. Subsequently, 25.0 g of the compound represented by the above formula (6-1) was added over 3 hours at the same temperature while dividing. After completion of the addition, the reaction was allowed to stir at the same temperature for 2 hours. After completion of the reaction, stirring was stopped and the mixture was allowed to stand overnight. The next day, the supernatant was removed by decantation and the same amount of water was added. 28 mass% aqueous ammonia was added to adjust the pH to 6.0, and then allowed to stand. After 1 hour, the supernatant was removed by decantation and the same amount of water was added. After standing again for 1 hour, the supernatant was removed by decantation, the same amount of water as the amount removed was added, and the crystals were filtered off using a 110 mm Nutsche. After washing with a sufficient amount of water, it was dried at 60 ° C. for 7 hours to obtain 44.7 g (yield 97.1%) of (Pig-1).
The purity of the formula (Pig-1) obtained in Examples 6 and 7, the amount of solvent that could be decanted, and the filterability were as shown in the table below. Purity measurement and filterability evaluation were performed in the same manner as in Examples 1-5.

[Example 8]
In a mixed solvent of 55.0 g of glacial acetic acid and 37.0 g of propionic acid, 15.0 g of the sulfate of the compound represented by the above formula (1) synthesized in Synthesis Example 3 was added and stirred. At this time, the system was a suspension. The suspension was cooled to 5 ° C., and 19.3 g of nitrosylsulfuric acid (43% by mass sulfuric acid solution) was added dropwise over 5 minutes. During this time, the internal temperature rose to 9 ° C. After completion of dropping, the temperature was raised to 25 ° C. to 30 ° C. and stirred for 1 hour at 150 rpm. After completion of the reaction, the reaction mixture was cooled to 25 ° C. or lower, and 0.3 g of urea was added in portions while maintaining the same temperature. The mixture was stirred for 15 minutes to obtain a diazonium compound preparation solution. This diazonium compound preparation solution was dropped at 3 ° C. or less into a solution in which 10.0 g of a compound represented by the following formula (7) was suspended in 150 g of acetone. After completion of the dropwise addition, the mixture was stirred at the same temperature for 2 hours to be reacted. After completion of the reaction, the crystals were separated by filtration. After washing with a sufficient amount of acetone and water, the mixture was suspended in 400 g of water and neutralized with an aqueous potassium hydroxide solution to pH 5.7. After stirring for 10 minutes, the crystals were filtered off using a 110 mm Nutsche. After washing with a sufficient amount of water, it was dried at 60 ° C. for 7 hours to obtain 17.1 g (yield 91%) of (Pig-2). The purity of the obtained (Pig-2) was 96.4%.

Claims (7)

A method for producing an azo pigment represented by the general formula (2), comprising the step (a) of obtaining a diazonium compound by mixing an acid salt of an amine represented by the formula (1) and a diazotizing agent. Because
Wherein step (a) is viewed contains the step of adding the diazotization agent in a solution of salt and acid of the amine, the diazotizing agent is nitrosylsulfuric acid, method for producing the azo pigment.

(In General Formula (2), R ₁ and R ₂ are each independently a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, or a 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, acylamino group, aminocarbonylamino group , Alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group, arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkylsulfinyl group, aryl Sulfinyl 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, Represents an imide group, a phosphoryl group, a sulfo group, a carboxyl group, a phosphono group, or a quaternary ammonium group, G represents a 5- to 6-membered heterocyclic group, and W represents a substituent that can be bonded to the heterocyclic group that G constitutes. Substituents that can be bonded to the heterocyclic group constituting G are a halogen atom, an alkyl group, a cycloalkyl group, an aralkyl group, an alkenyl group, an alkynyl group, an aryl group, a heterocyclic group, a cyano group, and a hydroxyl group. Nitro group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, Siloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkylsulfonylamino group , Arylsulfonylamino group, alkylthio group, arylthio group, heterocyclic thio group, sulfamoyl group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group Phosphino group, phosphinyl group, phosphinyloxy group, phosphinylamino group, silyl group, azo group, imide group, phosphoryl group, sulfo group, carboxyl group Represents a syl group, a phosphono group or a quaternary ammonium group. t represents an integer of 0 to 3. )   The method for producing an azo pigment according to claim 1, further comprising a step (b) of mixing and reacting the diazonium compound obtained in the step (a) with a coupling component.   Furthermore, the manufacturing method of the azo pigment of Claim 2 including the process (c) which adds water to the reaction liquid obtained at the process (b).   Mixing in the said process (a) is performed at 20 to 50 degreeC, The manufacturing method of the azo pigment of any one of Claims 1-3 characterized by the above-mentioned. The said azo pigment is an azo pigment represented by following formula (3), The manufacturing method of the azo pigment of any one of Claims 1-4 characterized by the above-mentioned.

  The method for producing an azo pigment according to any one of claims 1 to 5, wherein the acid salt is a sulfate. The method for producing an azo pigment according to any one of claims 1 to 6, wherein the acid salt is produced using a compound represented by formula (4) or formula (5) as a starting material.

(In general formula (4), R ₃ represents an alkyl group.)