TW202035576A - Azo pigment composition and manufacturing method thereof - Google Patents

Abstract

An object of the present invention is to provide an azo pigment composition and a method for producing the same, which can improve the luminance and contrast of a color filter compared to the conventional one and the print density (color development) of an inkjet type printed matter. To achieve the object, a method for producing an azo pigment composition is provided, wherein during the production of the azo pigment of the reaction product of a base represented by the following formula (1), and a coupler represented by the following formula (2), another base represented by the following formula (3) and another coupler represented by the following formula (4) are added. (In formula (1), R1 represents R3-NH-C(=O)-, R2 represents halogen atom or R4O-, R3 represents a hydrogen atom or a phenyl group (-C6H5), and R4 represents a C1-C4 alkyl group.) (In formula (2), R5 represents a hydrogen atom or -CONH-R6, and R6 represents the following formula (2-1).) (In formula (2-1), R7 represents R9-NH-C(=O)-, R8 represents halogen atom or R10O-, R9 represents a hydrogen atom or a phenyl group (-C6H5), R10 represents a C1-C4 alkyl group, and * represents a bond.) (In formula (4), R11 represents -SO3H or -COOH.).

Description

Azo pigment composition and its manufacturing method

The present invention relates to an azo pigment composition and a manufacturing method thereof.

Azo pigments are widely used as coloring agents for paints, offset inks, gravure inks, color toners, inkjet inks for recording, coloring agents for color filters, and the like. In these applications, in order to improve various characteristics such as brightness and contrast of the formed coating film, there are cases where finer azo pigments are used. However, it is generally known that a coloring composition containing a finer pigment tends to deteriorate in dispersion stability. Therefore, a document proposes a strategy for ensuring the dispersion stability of pigments and the like while improving these characteristics (Patent Documents 1 to 6).

Patent Document 1 describes the use of organic pigments, pigment dispersing aid A (which is a compound of a compound having the same skeleton as the organic pigment), a specific structure of pigment dispersing aid B, pigment dispersant, and organic solvents. During the manufacturing process of the red pigment dispersion for optical filters, the dispersing aid A is mixed with the organic pigment to be refined, and then the pigment dispersing aid B, pigment dispersant, and organic solvent are mixed and dispersed. A step of. It is believed that by using two kinds of pigment dispersing additives, the fine dispersion of the pigment and the subsequent dispersion stability can be improved, and excellent color characteristics, high light transmittance and contrast can be achieved.

Patent Document 2 describes a coloring composition for color filters, which is characterized by containing a colorant (A), which contains a red azo pigment having a maximum refractive index of 1.8 or less in the light wavelength region of 600 to 700 nm (a1); and resin (B). It is considered that when such a pigment (a1) is contained, the contrast is high and it is not necessary to make the pigment excessively finer, and therefore the stability is also excellent.

Patent Document 3 describes a method of adding a pigment dispersing aid having a specific structure, an acrylic system having a tertiary amine group and/or a quaternary ammonium group, to a particulate product obtained by micronizing a pigment containing CI Pigment Red 221 The block copolymer and an organic solvent are dispersed to obtain a pigment dispersion, which is then made into a red pigment dispersion resist composition for color filters. By this method, the dispersion stability of the fine particles of the pigment containing CI Pigment Red 221 can be improved compared with the prior art, and it can provide excellent dispersion stability, coloring power, contrast, brightness, heat resistance, and solvent resistance. Red pigment dispersion resist composition for color filters.

Patent Document 4 describes that naphthol red with a specific structure is surface-treated with a hydrophilic naphthol derivative or a hydrophilic phenol derivative with a specific structure to obtain naphthol red with excellent dispersibility, color development, and transparency. .

Patent Document 5 describes that in the manufacturing process of a monoazo red pigment composition containing a monoazo pigment with a specific structure and an azonaphthoic acid component with a specific structure, the coupling of the diazonium salt component and the coupler component A monoazo pigment with a specific structure is synthesized by the reaction. The azonaphthoic acid component is obtained by adding hydroxynaphthoic acid to the coupler component in advance during the coupling reaction. It also describes that the monoazo-based red pigment composition obtained in this way and the color toner using the composition can maintain the reflection characteristics of the monoazo-based red pigment in the yellow tone region and the reflection characteristics of the blue tone region Good, wide range of color reproduction, sufficient brightness and chroma, excellent transparency, light resistance, and dispersion.

Patent Document 6 describes an inkjet ink containing a specific polymer-bound pigment dispersed in an aqueous ink vehicle. Moreover, with this configuration, it is possible to provide an inkjet ink that can produce printed images with good gloss and durability without increasing the viscosity of the ink. [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2011-162722 A [Patent Document 2] JP 2012-198453 A [Patent Document 3] JP 2016-61979 A [Patent Document 4] JP 2016-108451 A [Patent Document 5] Japanese Patent Application Publication No. 2000-248191 [Patent Document 6] Japanese Patent No. 4532387

[The problem to be solved by the invention]

For example, in the field of display devices using color filters, or the field of inkjet inks for recording, the market demand for high image quality is very high. Even if the inventions described in Patent Documents 1 to 6 are adopted, there are still improvements. room. Therefore, the object of the present invention is to provide an azo pigment composition and a manufacturing method thereof, which can improve brightness and contrast more than before in the field of display devices using color filters. In addition, it also provides an azo pigment composition and a manufacturing method thereof, which can increase the printing density (color development) more than before in the field of inkjet inks for recording. [Means used to solve the problem]

In order to solve the aforementioned problems, the inventors delved and reviewed. As a result, it was found that when manufacturing a specific azo pigment, if a substrate and a coupler different from the substrate and the coupler are added to carry out the coupling reaction, for example, in the field of display devices using color filters, the resulting pigment composition The brightness and contrast of the coating film of the object, and, for example, in the field of inkjet inks for recording, the printing density (color development) of the printed matter containing the obtained pigment composition can be improved more than before. invention.

The first point of the present invention relates to a method for producing an azo pigment composition, which is based on the reaction product of the substrate represented by the following formula (1) and the coupler represented by the following formula (2). During manufacture, another substrate shown in formula (3) and another coupler shown in formula (4) are added.

(In formula (1), R ¹ represents R ³ -NH-C(=O)-, R ² represents a halogen atom or R ⁴ O-. R ³ represents a hydrogen atom or a phenyl group (-C ₆ H ₅ ). R ⁴ represents an alkyl group with 1 to 4 carbon atoms.)

(In formula (2), R ⁵ represents a hydrogen atom or -CONH-R ^6. R ⁶ represents the following formula (2-1).)

(In formula (2-1), R ⁷ represents R ⁹ -NH-C(=O)-, R ⁸ represents a halogen atom or R ¹⁰ O-. R ⁹ represents a hydrogen atom or a phenyl group (-C ₆ H ₅ ) . R ¹⁰ represents an alkyl group with 1 to 4 carbon atoms. * represents a bond.)

(In formula (4), R ¹¹ represents -SO ₃ H or -COOH.)

In the embodiment of the present invention, with respect to 100 parts by weight of the base represented by formula (1), 0.5 to 4 parts by weight of the base represented by formula (3) can be added, relative to 100 parts by weight of the coupler represented by formula (2) In parts by weight, 2-10 parts by weight of the coupler shown in formula (4) can be added.

In the embodiment of the present invention, it is possible to perform a miniaturization treatment so that the average primary particle size of the azo pigment is 25 to 70 nm. In addition, in this case, the refinement treatment can be performed in the presence of a pigment derivative.

The second point of the present invention relates to an azo pigment composition comprising an azo pigment which is a reaction product of a substrate represented by the following formula (1) and a coupler represented by the following formula (2) Pigment composition, and includes the reaction product of the base represented by formula (1) and (3) and the coupler represented by formula (2) and (4), the reaction product of formula (1) and formula (2) The content (solid content basis) is 80-95% by weight.

(In formula (1), R ¹ represents R ³ -NH-C(=O)-, R ² represents a halogen atom or R ⁴ O-. R ³ represents a hydrogen atom or a phenyl group (-C ₆ H ₅ ). R ⁴ represents an alkyl group with 1 to 4 carbon atoms.)

(In formula (2), R ⁵ represents a hydrogen atom or -CONH-R ^6. R ⁶ represents the following formula (2-1).)

(In formula (2-1), R ⁷ represents R ⁹ -NH-C(=O)-, R ⁸ represents a halogen atom or R ¹⁰ O-. R ⁹ represents a hydrogen atom or a phenyl group (-C ₆ H ₅ ) . R ¹⁰ represents an alkyl group with 1 to 4 carbon atoms. * represents a bond.)

(In formula (4), R ¹¹ represents -SO ₃ H or -COOH.)

In the present invention, the weight ratio ((1)/(3)) of the component from formula (1) to the component from formula (3) can be 90.6/9.4~98.9/1.1, and the component from formula (2) is The weight ratio ((2)/(4)) of the components derived from formula (4) can be 82.4/17.6-96.5/3.5. [Effects of Invention]

According to the present invention, an azo pigment composition and a manufacturing method thereof can be provided. For example, in the field of display devices using color filters, the brightness and contrast of a coating film containing the resulting pigment composition, and for example, in the field of recording In the field of inkjet inks, the printing density (color development) of inkjet printing materials can be improved more than ever.

The embodiments of the present invention will be described below.

The embodiment of the method for producing an azo pigment composition related to the present invention is the production of an azo pigment which is a reaction product of a substrate represented by the following formula (1) and a coupler represented by the following formula (2) At the same time, add another base shown in formula (3) and another coupler shown in formula (4). In addition, in the following, the base represented by formula (1) is referred to as the main base, and the coupler represented by formula (2) is referred to as the main coupler. In addition, there may be cases where the azo pigment obtained from the main base and the main coupler is called the main azo pigment.

(In formula (1), R ¹ represents R ³ -NH-C(=O)-, R ² represents a halogen atom or R ⁴ O-. R ³ represents a hydrogen atom or a phenyl group (-C ₆ H ₅ ). R ⁴ represents an alkyl group with 1 to 4 carbon atoms.)

(In formula (2), R ⁵ represents a hydrogen atom or -CONH-R ^6. R ⁶ represents the following formula (2-1).)

(In formula (2-1), R ⁷ represents R ⁹ -NH-C(=O)-, R ⁸ represents a halogen atom or R ¹⁰ O-. R ⁹ represents a hydrogen atom or a phenyl group (-C ₆ H ₅ ) . R ¹⁰ represents an alkyl group with 1 to 4 carbon atoms. * represents a bond.)

(In formula (4), R ¹¹ represents -SO ₃ H or -COOH.)

In this way, by adding the main base and main coupler and another base and coupler that make up a specific azo pigment, the brightness or contrast of the color filter or the printing density (color development) of inkjet printing can be improved. , Presumably because the presence of reaction products other than the main azo pigment produced by the presence of another substrate and coupler (hereinafter referred to as by-products) can inhibit the target azo pigment (main Azo pigments) crystallize and grow crystals. It is estimated that crystallization or crystal growth is suppressed, and aggregation of the main azo pigment is suppressed, and the brightness or contrast of the color filter or the printing density (color development) of inkjet prints can be improved.

The compound represented by the aforementioned formula (1) can be used as the main substrate. In formula (1), the bonding position of R ¹ and R ² is not particularly limited. R ^{1 should} just be NH ₂ -C(=O)- or C ₆ H ₅ -NH-C(=O)-. R ^{2 may} be a halogen atom or R ⁴ O-. The halogen atom may be any of a chlorine atom, a bromine atom, and the like. R ⁴ only needs to be an alkyl group having 1 to 4 carbon atoms, as long as it is methyl, ethyl, propyl or butyl. The propyl and butyl groups can be linear or branched. Examples of such substrates include 3-amino-4-methoxybenzaniline, 2-chloro-5-methoxyaniline, 3-chloro-6-methoxyaniline and the like.

The main coupler can use the substance represented by the aforementioned formula (2). In the formula (2), R ^{5 may} be a hydrogen atom or -CONH-R ⁶ . R ⁶ only needs to be a functional group represented by the aforementioned formula (2-1), and the bonding position of R ⁷ and R ⁸ in the formula (2-1) is not particularly limited. R ^{7 should} just be NH ₂ -C(=O)- or C ₆ H ₅ -NH-C(=O)-. R ^{8 may} be a halogen atom or R ¹⁰ O-. The halogen atom may be any one such as a chlorine atom and a bromine atom. R ¹⁰ only needs to be an alkyl group having 1 to 4 carbon atoms, as long as it is methyl, ethyl, propyl, or butyl. Propyl and butyl can be linear or branched. Examples of such couplers include N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthocarboxamide and β-naphthol.

The other substrate with respect to the aforementioned main substrate may be a compound represented by formula (3). In formula (3), the bonding position of the sulfonic acid group is not particularly limited. Such another substrate may include p-aminobenzoic acid (sulfonyl acid), o-aminobenzoic acid (anthranilic acid), and m-aminobenzoic acid. One type or two or more types can be used for another substrate.

The other coupler with respect to the aforementioned main coupler should just be a compound represented by formula (4). In formula (4), the bonding position of R ¹¹ is not particularly limited. R ^{11 may} be -SO ₃ H or -COOH, and -COOH is preferred. Examples of such another coupler include β-naphthol, BON acid, Shepherd acid, F acid and the like.

Another kind of substrate and coupler, as long as the main substrate and the main coupler are used for the coupling reaction. For example, (1) a diazotized solution formed by diazotizing a solution containing a main substrate and another substrate can be mixed with a coupler solution containing a main coupler and another coupler to perform a coupling reaction, (2 ) When mixing the diazotized solution containing the main substrate and the coupler solution of the main coupler to perform the coupling reaction, add the diazotized solution of another substrate different from the main substrate and the main coupler and another coupler The method of coupling reaction and other methods. The diazotization and coupling reaction of the substrate can be performed under well-known conditions.

The mixing ratio of the main substrate and another substrate can use the main azo pigment as the main colorant, while ensuring the characteristics of the main azo pigment, effectively suppressing the desired azo caused by the products from the other substrate and the coupler From the viewpoint of crystallization and crystal growth of the pigment, it is better to add 0.5-4 parts by weight of another base to 100 parts by weight of the main base.

For the same reason, the mixing ratio of the main coupler and the other coupler is preferably 2-20 parts by weight relative to 100 parts by weight of the main substrate.

After the coupling reaction, it is filtered, washed with water, and dried to obtain a dried product of the azo pigment composition. The dried product can be used directly as an azo pigment composition. The pulverized product obtained by pulverizing the dried product can also be used as an azo pigment composition. The fine product obtained by refining the dried product or the pulverized product can also be used as an azo pigment composition.

The pulverized product can be obtained by pulverizing it with a disperser such as a roll mill or a bead mill. In addition, the fine product can be obtained by, for example, a salt polishing method. The miniaturization by the salt grinding method, especially the solvent salt grinding method, can be achieved by, for example, mixing the dried or pulverized product of the pigment composition, water-soluble inorganic salt and water-soluble solvent, and then using a kneader, etc. The mixture is kneaded mechanically, and the pigment composition is ground with water-soluble inorganic salt. Such salt milling can use conventionally known conditions. After salt milling, water washing is performed to remove water-soluble inorganic salts and water-soluble solvents to obtain a finer pigment composition. It is better to wash with water until the water-soluble inorganic salt and water-soluble solvent are completely removed. It can also be dried to remove water due to application.

When performing the refining treatment, from the viewpoint of more effectively suppressing the crystallization or crystal growth of the azo pigment, the refining treatment may be performed in the presence of a surface treatment agent such as a pigment derivative or resin. For example, in the case of the aforementioned solvent salt grinding method, the surface treatment agent may be present when the pigment composition is ground with a kneader. The surface treatment agent may be added all at the beginning of kneading, or may be divided into multiple additions after kneading starts.

A pigment derivative is a compound in which an organic pigment is the basic skeleton and an acidic group or an aromatic group is introduced as a substituent in the side chain. As the organic pigment of the matrix skeleton, specifically, quinacridone pigments, phthalocyanine pigments, azo pigments, quinophthalone pigments, isoindoline pigments, isoindoline pigments, Quinoline pigments, diketopyrrolopyrrole pigments, benzimidazolone pigments, dioxazine pigments, etc. In addition, the matrix skeleton generally includes pale yellow aromatic polycyclic compounds such as naphthalene, anthraquinone, triazine, and quinoline that are not called pigments. For such pigment derivatives, for example, Japanese Patent Application Publication No. 11-49974, Japanese Patent Application Publication No. 11-189732, Japanese Patent Application Publication No. 10-245501, Japanese Patent Application Publication No. 2006-265528, Japanese Patent Application Publication No. 8- 295810, Japanese Patent Application Publication No. 11-199796, Japanese Patent Application Publication No. 2005-234478, Japanese Patent Application Publication No. 2003-240938, Japanese Patent Application Publication No. 2001-356210, Japanese Patent Application Publication No. 2007-186681, Japan Articles described in Japanese Patent Application Publication No. 2003-167112 and Japanese Patent Application Publication No. 2013-199470.

The addition amount of the pigment derivative (non-volatile matter or solid content) is preferably 1-20 parts by weight relative to 100 parts by weight of the pigment composition.

Examples of the resin of the surface treatment agent include vinyl ester resins, acrylic resins, and the like. The addition amount of the resin as the surface treatment agent is preferably 3 to 30 parts by weight relative to 100 parts by weight of the pigment composition.

In the miniaturized pigment composition, the average primary particle size of the azo pigment is preferably 25 to 70 nm. Such an average primary particle size can be arbitrarily selected from 50 micronized pigment particles, for example, from 50,000 times and 100,000 times images obtained by a transmission electron microscope (trade name: JEM-1011, manufactured by JEOL Ltd.) , Measure the maximum particle size of each micronized pigment particle according to the measuring rule shown in the image, and obtain the arithmetic average.

In the case of inkjet inks, the average particle diameter of the secondary particles of the pigment is preferably from the viewpoint of improving the dispersibility, and from the viewpoint of the ejectability of the ink ejection nozzles of the inkjet recording type printer. 300 nm or less, preferably 150 nm or less. The average particle size of the secondary particles of the pigment contained in the pigment composition used for inkjet inks means that the coloring composition for inkjet inks or the particles contained in the inkjet ink are measured by a laser zeta potentiometer. The measured value measured during the measurement.

In addition to being present during the refining treatment, the pigment derivative may be added and mixed after the refining treatment.

The embodiment of the azo pigment composition related to the present invention is an azo pigment comprising the reaction product of the base represented by the above formula (1) and the coupler represented by the above formula (2). In addition, it is a reaction product containing the substrate represented by the above formula (1) and (3) and the coupler represented by the above formula (2) and (4), and the reaction product of the formula (1) and formula (2) The content of the substance (based on solid content) is preferably 80-95% by weight. Such an azo pigment composition can be obtained by, for example, the aforementioned manufacturing method.

In the azo pigment composition obtained by the aforementioned manufacturing method, in addition to the main azo pigment of the reaction product produced by the coupling reaction between the diazonium compound of the main substrate and the main coupler, it also contains another substrate and Couplers participate in the by-products produced by the coupling reaction. It is thought that the crystallization and crystal growth of the main azo pigment will be suppressed by the by-products produced by the participation of the other substrate and the coupler as described above. From the viewpoint of exerting the function of the main azo pigment itself, and effectively exerting the function generated by the by-product, it can improve the brightness or contrast of the color filter or the print density (color development) of the inkjet printing method. In the past, the appropriate range of the content (solid content basis) of the main azo pigment is as described above. In other words, the content of by-products (solid content basis) is preferably 20 to 5 wt%.

In the case where a pigment derivative is used for the refinement treatment and when the pigment derivative is added after the refinement treatment, the azo pigment composition may contain the pigment derivative. In this case, the content (solid content basis) of the main azo pigment is preferably 64 to 94% by weight.

Regarding the composition of the main azo pigment and the by-products contained in the azo pigment composition, from the function of the by-product, the brightness and contrast of the color filter or the printing density of inkjet printing (color development) From the point of view of ), the weight ratio ((1)/(3)) of the component from formula (1) to the component from formula (3) is 90.6/9.4~98.9/1.1, and the component from formula (2) is The weight ratio ((2)/(4)) of the ingredients derived from formula (4) is preferably 82.4/17.6 to 96.5/3.5.

The composition of the main azo pigment and the by-products can be controlled by the composition ratio of the starting materials. However, the obtained azo pigment composition can also be used and determined by gas chromatography mass analysis (GC/MS).

The main azo pigment contained in the embodiment of the manufacturing method and the azo pigment composition related to the present invention is exemplified by the dye index number, and it is C.I. Pigment Red 269 and the like.

The azo pigment composition described above can be used as a coloring agent for paints, offset inks, intaglio inks, color toners, inkjet inks for recording, and coloring agents for color filters. Since the brightness and contrast can be improved more than before, it is particularly suitable as a coloring agent for color filters of image display devices. In addition, in recent years, in image display devices using color filters, various light sources such as cold cathode tubes, light-emitting diodes, and organic EL elements can be used as the light source for the backlight. However, they are pigments with strong coloring power, so any of them are used. The light source and color reproducibility are good, and good brightness can be obtained in various color gamuts. In addition, the print density (color development) can be improved more than before, so it is also suitable as a coloring agent for inkjet inks for recording.

Hereinafter, first, a case where the aforementioned azo pigment composition is used as a coloring agent for color filters is used as an example to describe the outline of a coloring composition for forming a coating film for color filters.

The coloring composition for forming a coating film contains the aforementioned azo pigment composition, a dispersant, a dispersion aid, a solvent, a coating film forming component, and other additives. Among these, dispersing aids, solvents, and other additives can be added as needed in accordance with the components of the azo pigment composition.

Examples of the dispersant include resin-type dispersants and surfactant-type dispersants. Specific examples of resin type pigment dispersants include, for example, polyurethane, polyester, unsaturated polyamide, phosphoric acid ester, polycarboxylic acid and its amine salt, ammonium salt, alkylamine salt, and polycarboxylate. , Hydroxy-containing polycarboxylate, polysiloxane, modified polyacrylate and other oily dispersants, (meth)acrylic acid. Water-soluble resins or water-soluble polymer compounds such as (meth)acrylate copolymers, (meth)acrylic-styrene copolymers, and styrene-maleic acid copolymers. Surfactant-type pigment dispersants include anionic active agents such as naphthalenesulfonic acid formalin condensate, aromatic sulfonic acid formalin condensate, polyoxyethylene alkyl phosphate, and nonionic active agents such as polyoxyethylene alkyl ether. Cationic agents such as alkylamine salts, quaternary ammonium salts, etc. The dispersant may contain one kind or two or more kinds. The content of the dispersant (solid content or active ingredient) is preferably 10 to 40 parts by weight relative to 100 parts by weight of the azo pigment composition from the viewpoint of dispersion stability.

Examples of the dispersion aid include the aforementioned pigment derivatives and dispersion resins. Pigment derivatives may be unnecessary when they are contained in the azo pigment composition. From the viewpoint of further improving the dispersion stability of the particles in the color composition, they may be further added. The content of the pigment derivative (solid content or active ingredient) is preferably 2 to 15 parts by weight relative to 100 parts by weight of the azo pigment composition from the viewpoint of dispersion stability. When the pigment derivative is contained in the azo pigment composition, it is based on the total amount. The dispersion resin is particularly suitable for use when the coating film forming component contains a photopolymerizable component. Examples of such dispersion resins include alkali-soluble resins described later. The dispersion resin and the alkali-soluble resin used as the coating film forming component may be the same type of resin or different types of resins. The content of the dispersion resin is preferably 10 to 50 parts by weight relative to 100 parts by weight of the total of the pigment composition and the pigment derivative.

Examples of the solvent include various organic solvents such as aromatic, ketone, ester, glycol ether, alcohol, and aliphatic solvents. These solvents can be appropriately selected in accordance with the types of coating film forming components and the like. From the viewpoint of usability, the addition amount of the solvent can be added so that the concentration of the solid content including the azo pigment composition and the like becomes 10 to 30% by weight.

The coating film forming components include, for example, thermoplastic urethane resins, (meth)acrylic resins, polyamide resins, polyimide resins, styrene and maleic acid resins, and polyester resins. , Polymers such as silicone resins, cardo resins, and polymerizable components such as photopolymerizable components. The polymer is preferably an alkali-soluble resin that exhibits solubility in a solution in an alkali region. The content in the coloring composition of the polymer is preferably 10-40% by weight in the total solid content of the coloring composition. When the aforementioned dispersion resin is used, the total amount is used. The photopolymerizable component includes a photopolymerizable compound and a photopolymerization initiator. As such a photopolymerizable compound and photopolymerization initiator, for example, those described in JP 2009179789 A can be used. The content of the photopolymerizable compound in the coloring composition is preferably 5 to 70% by weight relative to all the nonvolatile components in the coloring composition. The content of the photopolymerization initiator in the coloring composition is relative to the coloring composition. All non-volatile components of the composition are preferably 0.1-10% by mass.

Other additives include other pigments, dyes, sensitizers (sensitizing dyes), chain transfer agents, fluorine-based organic compounds, thermal polymerization initiators, thermal polymerization components, fillers, surfactants, adhesion promoters, Antioxidant, anti-aggregation agent, surface regulator (leveling agent), etc. Other pigments or dyes are pigments or dyes used in combination with the aforementioned main azo pigment for toning.

The coloring composition for coating film formation can be obtained by adding the aforementioned components to a well-known dispersing machine such as a bead mill, a sand mixer, and a dispersing machine and dispersing it. In addition, the method of adding each ingredient can be to mix and disperse all the ingredients, mix and disperse several of the ingredients, and then add the remaining ingredients in one or more divisions and make them dispersed . For example, a pigment dispersion containing an azo pigment composition, a dispersant, and a solvent, and if necessary, a dispersion aid, can be prepared, and a coating film forming component and necessary additives can be added to the dispersion, and then dispersed.

Next, a case where the aforementioned azo pigment composition is used as a coloring agent for inkjet ink for recording is used as an example to describe the outline of the coloring composition for inkjet ink and the inkjet ink.

The coloring composition for inkjet ink contains the aforementioned azo pigment composition, dispersant, dispersion aid, solvent, and other additives. Among these, dispersing aids, solvents, and other additives can be added as necessary according to the components of the azo pigment composition.

The dispersant can be the same as in the case of the aforementioned coloring composition for forming a coating film, for example. In addition, for example, a resin-type dispersant containing a copolymer containing a cyclohexyl methacrylate unit and an acrylic acid unit described in International Publication No. 2012/118078 can be used. The content of the dispersant (solid content or active ingredient) is preferably 10 to 40 parts by weight relative to 100 parts by weight of the azo pigment composition from the viewpoint of dispersion stability.

Examples of the dispersion aid include the aforementioned pigment derivatives. As in the case of the aforementioned coloring composition for forming a coating film, when a pigment derivative is contained in the azo pigment composition, it can be added as necessary. The content of the pigment derivative (solid content or active ingredient), from the viewpoint of dispersion stability, is preferably 2 to 14 parts by weight relative to 100 parts by weight of the azo pigment composition. When the pigment derivative is contained in the azo pigment composition, it is based on the total amount.

As the solvent, either an organic solvent or an aqueous solvent can be used.

Organic solvents, organic solvents other than aqueous solvents can be widely used. Alcohols, ketones, esters, glycol ethers, glycol acetates, saturated hydrocarbons, unsaturated hydrocarbons commonly used in inkjet inks , Cyclic saturated hydrocarbons, cyclic unsaturated hydrocarbons, aromatic hydrocarbons and other organic solvents.

Aqueous solvents include water and/or water-soluble organic solvents. As the water, pure water or ultrapure water such as ion exchange water, ultrafiltered water, reverse osmosis water, and distilled water can be used. The water-soluble organic solvent is not particularly limited as long as it is a water-soluble organic solvent generally used for inkjet ink applications. Specifically, solvents with a lower vapor pressure than water include, for example, polyols such as diethylene glycol, polyol ethers such as triethylene glycol monobutyl ether, ketones, esters, and lower alkoxy alcohols. Classes, amines, amides, heterocycles, stubbles, stubbles, etc. In addition, in order to prevent the appearance of mold, bacteria, etc., a solvent that is sterilized by ultraviolet treatment, hydrogen peroxide water treatment, or the like can also be used. Here, water solubility means that it can be mixed with water or exhibit a solubility in water of 3.3 g/100 mL or more at 20°C.

The content of the solvent is not particularly limited, and it can be set at approximately 200 to 600 parts by weight relative to 100 parts by weight of the pigment composition (solid content).

Other additives include other pigments or dyes, surface tension adjusters or penetrants (surfactants), anti-wetting and drying agents, preservatives, bactericides, pH adjusters, rust inhibitors, and humectants. These can be used alone or in combination of two or more as necessary.

The pH adjuster is not particularly limited as long as it can be controlled to a desired pH, and well-known drugs can be used. Examples include organic amines such as methylamine and ethylamine; lower alkanolamines such as monoethanolamine, diethanolamine, and triethanolamine; and inorganic bases such as ammonium hydroxide, sodium hydroxide, and potassium hydroxide.

In addition, the viscosity of the coloring composition for inkjet ink measured according to the method described later is preferably about 2-50 mPa･s. Thereby, the inkjet ink containing the coloring composition for inkjet ink can maintain a low viscosity, the inkjet ink can be ejected from the nozzle more stably, and better inkjet performance can be obtained.

In addition, the coloring composition for inkjet inks, especially when an aqueous solvent is used, preferably has a pH of about 7-10. Thereby, the storage stability of the coloring composition for inkjet ink becomes better.

The manufacturing method of the coloring composition for inkjet ink is not specifically limited, For example, the method of adding the said azo pigment composition, a dispersing agent, and other arbitrary components, and dispersing by a disperser/high-speed disperser etc. are mentioned. In addition, it can be dispersed by a bead mill or a roll mill as necessary. Furthermore, in order to remove particles of a certain size or more that may be contained in the finally obtained coloring composition for inkjet ink, filter filtration or centrifugal separation is performed. In addition, when performing filter filtration, the pore size (mesh size) of the filter may be appropriately selected as necessary to adjust the particle size of the particles contained in the coloring composition for inkjet ink to a predetermined particle size. Of course, filter filtration can be performed at the stage of preparing the coloring composition for inkjet ink, but it can also be performed at the stage of preparing the inkjet ink, or at the time of preparing the coloring composition for inkjet ink and inkjet ink. All stages are carried out.

The inkjet ink includes, for example, an ink obtained by adding solvents and surfactants that are conventionally known as components contained in inkjet inks to the aforementioned coloring composition for inkjet inks, and adding other additives as necessary. The content of each component contained in the inkjet ink is not particularly limited. The content of the pigment composition (solid content) is preferably about 2-10% by weight, and the content of the dispersant is preferably about 1-10% by weight. The solvent The content is preferably about 70-97% by weight.

The manufacturing method of the inkjet ink is not particularly limited. For example, it can be obtained by adding a solvent, a surfactant, and other additives to the coloring composition for an inkjet ink as necessary, and mixing and stirring. The method of mixing and stirring is not particularly limited, and a general mixer can be used, or a bead mill can be used to further improve the dispersibility of the pigment. If necessary, a filter can be used to remove particles of a certain size or more that may be contained in the ink.

The aforementioned inkjet ink contains a predetermined azo pigment composition, and therefore has an excellent printing density (color development) when used as a recording ink. For the print density (color development), for example, the measured value of the optical density (OD) described later can be used as an index. When the optical density (OD) is 1.1 to 1.3, it can be judged to have excellent print density. [Example]

The following examples illustrate the embodiments of the present invention in more detail.

(Production Example 1) Production of Pigment Derivative (I). 20 parts by weight of CI Pigment Yellow 138 (Paliotol Gelb K0961HD manufactured by BASF), 98% sulfuric acid, and 300 parts by weight were added to a 500ml separable flask, and the temperature The reaction was carried out for 5 hours to obtain the phthalimide quinophthalone compound. The reaction mixture was poured into 3000 parts of water under stirring to precipitate the phthalimide quinophthalone compound and after stirring for 30 minutes, filtration and water washing were repeated three times. After the obtained wet cake was washed with 300 parts by weight of 1% dilute sulfuric acid, it was filtered and washed with water. It was dried in a hot air dryer to obtain 54 parts by weight of the pigment derivative (I) represented by the following formula (5). As a result of mass analysis of the obtained pigment derivative (I) by the liquid chromatography mass analyzer "LC/MS" (Electro Spray Ionization) manufactured by Hewlett Packard, m/z 733 [MH] was detected ^- . As a result of elemental analysis and mass analysis of the pigment derivative (I), p=0.8.

(Example 1) Disperse 50 g (0.21 mol) of 3-amino-4-methoxybenzylaniline and 1.2 g (0.0069 mol) of sulfonic acid as another base in 1000 g of water, add ice, and adjust the temperature The conditions were set at 0~5°C, 55 g (0.53 mol) of 35% hydrochloric acid aqueous solution was added and stirred for 30 minutes. Then, 50 g (0.22 mol) of a 30% sodium nitrite aqueous solution was added, and after stirring for 60 minutes, 1.2 g (0.012 mol) of sulfamic acid for removing excess nitrous acid was added. Furthermore, 40 g (0.29 mol) of sodium acetate and 58 g (0.87 mol) of 90% acetic acid were added to prepare a diazonium salt solution. In addition, 64 g (0.1954 mol) of N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthylcarboxamide and 4.4 g (0.0235 mol) of BON acid as another coupler ) Dissolve together with 1000 g of water and 25 g (0.63 mol) of caustic soda at a temperature below 80°C to prepare a coupler solution. This solution was added to the above-mentioned diazonium salt solution under a temperature condition of 10°C or less to perform a coupling reaction, and heat treatment was performed at 90°C. This reaction mixture was filtered and washed with water, and then dried at 100°C. Then, the dried product was pulverized to obtain a pulverized product. The reaction product of the diazonium compound of 3-amino-4-methoxybenzamide and N-(5-chloro-2-methoxyphenyl)-3-hydroxy-2-naphthalenecarboxamide The content of Pigment Red 269 is 89.1% by weight. The weight ratio ((1)/(3)) of the components from the main substrate (1) and the other substrate (3) is 97.1/2.9, and the ratio of the components from the main coupler (2) and the other coupler (4) The weight ratio ((2)/(4)) is 91.7/8.3.

The obtained pulverized product is subjected to a refining treatment as described below to obtain a refined azo pigment composition. That is, 300 g of ground material, 45 g of surface treatment agent (Ripoxy (registered trademark) SPC2000, Showa Denko Co., Ltd., vinyl ester resin), 3000 g of Glauber's salt as an attritor, and ethylene glycol (Nippon Shokubai Co., Ltd. Co., Ltd.) 800 g was put into a double-arm kneader (5L kneader Σ type manufactured by Moriyama, hereinafter referred to as a kneader), the temperature was controlled so that the temperature of the kneaded product in the kneader was 40°C, and the kneading was performed for 9 hours. After the kneading is over, the kneaded material is taken out and moved to a temperature-adjustable tank with 16L of deionized water in advance, stirred with a stirring device at 180rpm for 30 minutes, and adjusted to pH 2.3~2.5 with 35% hydrochloric acid. Stir for further 1 hour to disperse the kneaded product. The dispersion was transferred to a suction filter and filtered, and the residue was washed with deionized water until the conductivity of the washing drainage became 3 μS/cm or less. The residue containing moisture after washing with water was taken out, placed in a drying shelf (material SUS304), and moved to a dryer to be dried at 95°C for 20 hours. The dried product was pulverized with a pulverizer (small pulverizer manufactured by Kyoritsu Riko Co., Ltd., sample grinder SK-M2) to obtain a fine powdered azo pigment composition. The particles in the refined azo pigment composition have an average primary particle size of 50 nm.

(Example 2) Except that the addition amount of sulfonic acid was set to 0.7 g (0.0040 mol) and the addition amount of BON acid was set to 2.5 g (0.013 mol), in the same manner as in Example 1, a fine powder was obtained. Azo pigment composition. The content of Pigment Red 269 is 93.6% by weight. The weight ratio ((1)/(3)) of the components from the main substrate (1) and the other substrate (3) is 98.3/1.7, and the ratio of the components from the main coupler (2) and the other coupler (4) The weight ratio ((2)/(4)) is 95.2/4.8. The average primary particle diameter of the particles in the refined azo pigment composition was 55 nm.

(Example 3) Except for using 5.8 g (0.0235 mol) of sodium sheferrous sodium instead of 4.4 g (0.0235 mol) of BON acid, a fine powdered azo pigment composition was obtained in the same manner as in Example 1. The content of Pigment Red 269 is 88.1% by weight. The weight ratio ((1)/(3)) of the components from the main substrate (1) and the other substrate (3) is 97.1/2.9, and the ratio of the components from the main coupler (2) and the other coupler (4) The weight ratio ((2)/(4)) is 90.6/9.4. The average primary particle diameter of the particles in the refined azo pigment composition was 65 nm.

(Example 4) Except that 5.3 g (0.0235 mol) of F acid was used instead of 4.4 g (0.0235 mol) of BON acid, in the same manner as in Example 1, a fine powdered azo pigment composition was obtained. The content of Pigment Red 269 is 88.5% by weight. The weight ratio ((1)/(3)) of the components from the main substrate (1) and the other substrate (3) is 97.1/2.9, and the ratio of the components from the main coupler (2) and the other coupler (4) The weight ratio ((2)/(4)) is 91.1/8.9. The average primary particle diameter of the particles in the refined azo pigment composition is 60 nm.

(Comparative example 1) Except that the sulfonic acid and the BON acid were not added, a dried product was obtained in the same manner as in Example 1, and then the refining treatment was performed to obtain a powdery azo pigment composition. The average primary particle diameter of the particles in the obtained azo pigment composition was 90 nm.

(Comparative example 2) Except that the BON acid was not added, a dried product was obtained in the same manner as in Example 1, and then the refining treatment was performed to obtain a powdery azo pigment composition. The average primary particle diameter of the particles in the obtained azo pigment composition was 100 nm.

(Comparative example 3) Except that the sulfonic acid was not added, a dried product was obtained in the same manner as in Example 1, and then the refining treatment was performed to obtain a powdery azo pigment composition. The average primary particle diameter of the particles in the obtained azo pigment composition was 120 nm.

(Comparative Example 4) Except that 0.95 g (0.0069 mol) of p-aminobenzoic acid was used instead of 1.2 g (0.0069 mol) of sulfonyl acid, a dried product was obtained in the same manner as in Example 1, and then subjected to a micronization treatment to obtain a powder. Azo pigment composition. The content of Pigment Red 269 is 87.8% by weight. The weight ratio ((1)/(3)) of the components from the main substrate (1) and the other substrate (3) is 97.3/2.7, and the ratio of the components from the main coupler (2) and the other coupler (4) The weight ratio ((2)/(4)) is 91.7/8.3. The average primary particle diameter of the particles in the obtained azo pigment composition was 80 nm.

(Comparative Example 5) Except that 3.4 g (0.0235 mol) of β-naphthol was used instead of 4.4 g (0.0235 mol) of BON acid, a dried product was obtained in the same manner as in Example 1, and then refined to obtain a powdery azo pigment Composition. The content of Pigment Red 269 is 89.8% by weight. The weight ratio ((1)/(3)) of the components from the main substrate (1) and the other substrate (3) is 97.1/2.9, and the ratio of the components from the main coupler (2) and the other coupler (4) The weight ratio ((2)/(4)) is 92.4/7.6. The average primary particle diameter of the particles in the obtained azo pigment composition was 110 nm.

(Test Case 1) ＜Preparation of pigment dispersion A1~9＞ The azo pigment composition obtained in Examples 1 to 4, Comparative Examples 1, 2, and 5: 22.5% by weight, and the pigment derivative (I) obtained in Production Example 1: 2.5% by weight (relative to the azo pigment composition (11.1% by weight) (hereinafter, the azo pigment composition and the pigment derivative (I) may be combined as the colorant component), polymer dispersant (Disperbyk LPN-21715 manufactured by BYK-Chemie Japan) ): Solid content is 28% by weight relative to the colorant component, polymer-based dispersant (Disperbyk 111 manufactured by BYK-Chemie Japan): Solid content is 2% by weight relative to the colorant component, dispersing resin (Soken Chemical Co., Ltd. Follett (registered trademark) ZAH110 manufactured by the company, solid content 35.0%, alkali solubility): solid content is 20% by weight relative to the colorant component, propylene glycol monomethyl ether (PM) as a solvent: 10% by weight, propylene glycol as a solvent Monomethyl ether acetate (PMA): The remaining part is added to a blender (single-shaft mixer) with an inner volume of 550 ml and stirred for 10 minutes. Next, 480 g of zirconia beads (Toray ceram crushed balls manufactured by Toray Co., Ltd.) with an average particle diameter of 0.8 mm were added, and stirred in a 40°C thermostat for 30 minutes to perform dispersion treatment. Then, PMA was added to make the azo pigment composition 20% by weight, and stirring was performed for 10 minutes, and the zirconia beads were removed by filtration. Next, add zirconia beads (Toray ceram pulverized balls manufactured by Toray Co., Ltd.) with an average particle diameter of 0.1 mm in an amount that is 4 times the total charged amount in terms of weight, and stir for 50 minutes in a constant temperature bath at 40°C. Disperse processing. Then, PMA was added to make the azo pigment composition 15% by weight, and the mixture was stirred for 10 minutes. Using a filter (PALL HDCII Membrane Filter manufactured by PALL), the zirconia beads were removed by filtration to obtain a pigment dispersion A1 ~6, 9.

When the azo pigment compositions obtained in Comparative Examples 3 and 4 were used for dispersion treatment in the same manner, they were colloidal, and the desired pigment dispersions A7 and 8 could not be obtained. Therefore, the following evaluation was not performed.

＜Evaluation＞ ＜＜Formation of coating film＞＞ In the pigment dispersions A1 to 6, 9 are added so that the azo pigment composition becomes 12% by weight, and the total amount of the dispersion resin and polymer dispersant is 100% by weight relative to the azo pigment composition Coating film forming components (Follett (registered trademark) ZAH110 manufactured by Soken Chemical Co., Ltd., acrylic polymer, solid content 35.0%, alkali solubility) and PMA were used to prepare coloring compositions A1 to 6, 9. The obtained coloring compositions A1 to 6, 9 were applied to a glass plate having a thickness of 1 mm and a square of 100 mm using a spin coater (spin coater MS-150A manufactured by MIKASA Co., Ltd.). At this time, each coloring composition A1 to 6, 9 was coated by forming three coating films with different chromaticities x to produce three coated plates. That is, by changing the rotation speed of the spin coater and changing the thickness, the chromaticity x of one of the three sheets must be less than 0.6850, and the chromaticity x of the other sheets must be greater than 0.6850. The obtained coated sheet was preliminarily dried (Prebake) at 90°C for 2.5 minutes, and further dried at 230°C for 30 minutes (Postbake).

＜＜Measurement of chromaticity y, brightness y and contrast＞＞ For each coating film after Prebake and Postbake, a colorimeter (U3310 manufactured by Hitachi, Ltd.) was used to obtain the tristimulus value of the xyY colorimetric method. Regarding the contrast (CR ratio), it was obtained using a color brightness meter (TOPCON TECHNOHOUSE Co., Ltd., BM-5AS). For each coating film, an approximate straight line (calibration curve) was obtained from the measured values of the three coated plates prepared as described above, and the chromaticity y (Ry) and the brightness Y (when the chromaticity x (Rx) was 0.6850 The value of RY) is taken as the result of each coating film. Based on the coating film A1 obtained by using the coloring composition A1, the difference of RY (RY(A2~6,9)-RY(A1)) and CR ratio (A2 ~6, 9/A1). The results are shown in Table 1.

(Test Case 2) <Preparation of Pigment Dispersion B> In order to evaluate the hue (Rx, Ry) by combining brightness and contrast, a pigment dispersion B containing a yellow pigment for toning was prepared as described below. First, CI Pigment Yellow 139 (Irgaphor Yellow S2150CF, manufactured by BASF) was used as the yellow pigment for toning. This yellow pigment was used instead of the azo pigment composition obtained in Example 1. In addition, it was combined with the pigment Dispersion A similarly obtained a yellow pigment dispersion (Y) for toning. Next, the pigment dispersions A1 to 6, 9 (R) and the yellow pigment dispersion (Y) for toning were mixed at the mixing ratio (R/Y, weight basis) of Table 2 to prepare pigment dispersion B (CI The total of pigment yellow 139 and coloring agent components is 15% by weight, and the solid content is 22.50%).

＜Evaluation＞ Using the obtained pigment dispersions B1 to 6 and 9, the coloring compositions B1 to 6, 9 and coating films B1 to 6, 9 were prepared in the same manner as in Test Example 1, and the chromaticity y (Ry), Brightness Y (RY), contrast (CR), and evaluate. The results are shown in Table 2.

It can be seen from Tables 1 and 2 that when manufacturing azo pigments of the reaction product of a specific substrate and coupler, by adding a specific substrate and coupler that are different from the substrate and coupler, it can provide a method that is different from the previous manufacturing method. Compared with the obtained azo pigment and the azo pigment composition, the azo pigment composition can form a coating film superior in contrast and brightness.

(Production Example 2) Production of polymer type dispersant A 1000 ml separable flask equipped with a stirring device, a condenser, a thermometer, and a dropping funnel was replaced with nitrogen, and then 200 parts by weight of butyl acetate was added to the separable flask, and the temperature was raised to 100°C with stirring. Next, add 200 parts by weight of butyl acetate, 252 parts by weight of cyclohexyl methacrylate (CHMA), 4 parts by weight of styrene (St), 56 parts by weight of butyl acrylate (BA), and acrylic ( AA) 88 parts by weight and 14 parts by weight of azobisisobutyronitrile were dropped into a separable flask at 100°C for 4 hours. After the dripping is finished, keep for 1 hour to finish the reaction. The end of the reaction is judged by measuring the unreacted monomer in the reaction solution by gas chromatography. Then, butyl acetate was removed by distillation under reduced pressure to obtain a copolymer. The obtained copolymer contained monomers in a weight ratio of CHMA/BA/AA/St=63/14/22/1, an acid value of 160 mg-KOH/g, and a weight average molecular weight of 5,300. Use this copolymer as a dispersant.

(Evaluation) ＜Measurement of average particle size＞ Using a laser zeta potentiometer (ELS-8000, manufactured by Otsuka Electronics Co., Ltd.), the average particle diameter of the particles contained in the inkjet ink obtained in Example 5 was measured.

＜Measurement of viscosity＞ Using a TV-22 viscometer manufactured by Toki Sangyo Co., Ltd., the viscosity of the inkjet ink obtained in Example 5 was measured at 25°C.

＜pH measurement＞ The pH of the inkjet ink obtained in Example 5 was measured at 25°C using a pH meter F-54 manufactured by Horiyang Manufacturing Co., Ltd.

＜Evaluation of printing density＞ Using the inkjet ink obtained in Example 5, full-page printing was performed on plain paper (double-sided plain paper manufactured by Seiko Epson Co., Ltd.) with an inkjet printer, and the print density was measured (optical density: OD) , As an indicator of color development. The optical density (OD) is GRETAG (registered trademark) RD-19 manufactured by GretagMacbeth, and the OD is measured 5 times for each sample, and the average value is used.

(Example 5) 15 parts by weight of the micronized azo pigment composition produced in Example 1, 4.50 parts by weight (solid content) of the dispersant obtained in Production Example 2, and 0.45 parts by weight of a 30% aqueous sodium hydroxide solution as a pH adjuster, 1.35 parts by weight of triethanolamine as a pH adjuster, 0.2 parts by weight of Biokiller LS (manufactured by KI Chemical Co., Ltd.) as a preservative and antifungal agent, and 0.05 parts by weight of BYK024 (manufactured by BYK-Chemie Japan) as a defoaming agent Mix and add ion-exchange water to make the pigment content 20% by weight, and stir with a high-speed disperser for 1 hour to obtain a pigment dispersion slurry. The pigment dispersion slurry was put into a cylindrical container filled with zirconia beads with a diameter of 0.65 mm, and dispersion treatment was performed in a mixer at a rotation speed of 2000 rpm for 1.5 hours to obtain a pigment dispersion. The obtained pigment dispersion was filtered with a filter with a pore diameter of 5 μm (manufactured by F-TECH Co., Ltd.) to obtain a coloring composition for inkjet ink. Ion-exchanged water was added to the obtained coloring composition for inkjet ink so that the pigment concentration was 15% by weight to prepare an aqueous inkjet ink. The aforementioned evaluation was performed using the obtained inkjet ink. As a result, the average particle diameter: 159 nm, viscosity: 8.2 mPa･s, pH: 9.9, and OD: 1.17, which are good results for inkjet inks.

Claims (6)

A method for producing an azo pigment composition, which is based on the following formula (1) and the following formula (2) of the reaction product of the reaction product of the azo pigment, adding formula (3) ) Shows another substrate and another coupler shown in formula (4),

(In formula (1), R ¹ represents R ³ -NH-C(=O)-, R ² represents a halogen atom or R ⁴ O-, R ³ represents a hydrogen atom or a phenyl group (-C ₆ H ₅ ), R ⁴ represents an alkyl group with 1 to 4 carbons)

(In formula (2), R ⁵ represents a hydrogen atom or -CONH-R ⁶ , and R ⁶ represents the following formula (2-1))

(In formula (2-1), R ⁷ represents R ⁹ -NH-C(=O)-, R ⁸ represents a halogen atom or R ¹⁰ O-, and R ⁹ represents a hydrogen atom or a phenyl group (-C ₆ H ₅ ) , R ¹⁰ represents an alkyl group with 1 to 4 carbons, * represents bonding)

(In formula (4), R ¹¹ represents -SO ₃ H or -COOH). The method for producing an azo pigment composition according to claim 1, wherein, relative to 100 parts by weight of the base shown in formula (1), 0.5 to 4 parts by weight of the base shown in formula (3) is added, relative to formula (2) 100 parts by weight of the coupler shown in ), add 2-10 parts by weight of the coupler shown in formula (4). The method for producing an azo pigment composition of claim 1 or 2, wherein the micronization treatment is performed to make the average primary particle diameter of the azo pigment 25 to 70 nm. The method for producing an azo pigment composition of claim 3, wherein the miniaturization process is performed in the presence of a pigment derivative. An azo pigment composition, which is an azo pigment composition comprising an azo pigment as a reaction product of a substrate represented by the following formula (1) and a coupler represented by the following formula (2), and comprising the formula The reaction product of the substrate shown in (1) and (3) and the coupler shown in formulas (2) and (4), and the content of the reaction product of formula (1) and formula (2) (solid content basis) 80~95% by weight,

(In formula (1), R ¹ represents R ³ -NH-C(=O)-, R ² represents a halogen atom or R ⁴ O-, R ³ represents a hydrogen atom or a phenyl group (-C ₆ H ₅ ), R ⁴ represents an alkyl group with 1 to 4 carbons)

(In formula (2), R ⁵ represents a hydrogen atom or -CONH-R ⁶ , and R ⁶ represents the following formula (2-1))

(In formula (2-1), R ⁷ represents R ⁹ -NH-C(=O)-, R ⁸ represents a halogen atom or R ¹⁰ O-, and R ⁹ represents a hydrogen atom or a phenyl group (-C ₆ H ₅ ) , R ¹⁰ represents an alkyl group with 1 to 4 carbons, * represents bonding)

(In formula (4), R ¹¹ represents -SO ₃ H or -COOH). Such as the azo pigment composition of claim 5, wherein the weight ratio ((1)/(3)) of the component from formula (1) to the component from formula (3) is 90.6/9.4~98.9/1.1, from The weight ratio ((2)/(4)) of the component of formula (2) to the component from formula (4) is 82.4/17.6 to 96.5/3.5.