TW201033292A - Azo pigment or its tautomers, its manufacturing method, pigment dispersant, colouring composition, ink for ink-jet recording, colouring composition for color filter and color filter - Google Patents

Abstract

The purpose of the present invention is to provide an azo compound, azo pigment, azo pigment dispersant and colouring composition, which has excellent color properties of tinting strength, tone and the like, and also has great fastness (especially solvent resistance). An azo pigment represented by following formula (1), its tautomers, salts, hydrate or solvate, which the said formula (1) has a characteristic X rays peak at the angles of 7.1 DEG, 25.3 DEG, 26.0 DEG and 27.2 DEG of Bragg's angles (2 θ ± 0.5 DEG) of the CuK α characteristic X rays diffraction.

Description

201033292 VI. Description of the invention: The invention relates to novel nitrogen-containing heterocyclic azo compounds, azo pigments, pigment dispersions containing the azo pigments, coloring compositions, inkjet recordings A coloring composition for color inks and color filters, and a color filter. [Prior Art] In recent years, as an image recording material, in particular, a material for forming a color image is mainly used, specifically, an inkjet recording material, a thermal transfer printing type recording material, and an electrophotographic recording material. Transfer-type silver halide photosensitive materials, printing inks, stylus pens, etc. are vigorously utilized. Further, in an image pickup device such as a CCD of a photographing machine, a color filter is used for recording and reproducing a color image in an LCD or a PDP of a display. In such color image recording materials or color filters, in order to display or record a full-color image, a so-called additive color mixing method or a subtractive color mixing method of three primary colors of pigments (dyes or pigments) is used, but it is achievable. The absorbing properties of the color reproduction range, and the sturdy® pigment which can withstand various use conditions and environmental conditions are not in actual conditions, and it is strongly desired to improve. The dyes or pigments used in each of the above applications must have the following properties in common. That is, it has excellent absorption properties in color reproducibility, and is excellent in fastness under use environment conditions, such as light resistance, heat resistance, and resistance to oxidizing gases such as ozone. Further, when the pigment is a pigment, it is also required to have good chemical fastness which is substantially insoluble in water or an organic solvent, and it does not impair the properties such as good absorption characteristics in a state in which the molecule is dispersed even when used as a particle. The above-mentioned required characteristics can be controlled by the strength of the interaction between the intermolecular -4- 201033292, but since the two are in a trade-off relationship, it is difficult to coexist. Further, when using a pigment, it is necessary to have a particle size and a particle shape necessary for exhibiting desired transparency, and to be fast under the environmental conditions to be used, such as light resistance, heat resistance, and oxidation to ozone. Gas resistance, good chemical resistance to other organic solvents or sulfurous acid gas, etc. 'disperse into fine particles in the medium to be used, and the dispersion state is a property such as stability. In particular, it is strongly desired to have a good hue, © in reactive gases in light, damp heat and the environment, especially pigments which have a high coloring power and are strong against light. That is, 'the required performance of the pigment is compared with the dye which is required as the performance of the dye molecule. 'It is involved in many aspects, not only as the performance of the dye molecule' but also completely satisfies the solid (fine particle dispersion) which is an aggregate of the pigment molecules. The above requirements are required. As a result, the compound group 'as compared with the dye' which is usable as a pigment is extremely limited, and even if the pigment is derivatized with a high-performance dye, the number of required properties as a fine particle dispersion is small, and it is not easy to develop. By. This can also be confirmed by the fact that the number of pigments registered by the color index is less than 1/10 of the number of dyes. Azo pigments are widely used in printing inks, inkjet inkjets, electrophotographic materials, etc. because of their excellent hue and coloring properties. Among these, the most commonly used azo pigments are the Diary Hde YeHow pigment and the naphthol red azo pigment. Examples of the benzidine pigment include c.i. Pigment Yellow 12, the same 13, and the same 17. Examples of the naphthol azo pigment include C.L pigment red 208' and 242. However, these pigments are very fast in 201033292, especially in light fastness, and the printed matter is decomposed and faded by exposure, and is not suitable for long-term storage of printed materials. In order to improve such a disadvantage, an azo pigment which improves the fastness by increasing the molecular weight or introducing a group having strong intermolecular interaction is also disclosed (see, for example, Patent Documents 1 to 3). However, even in the pigment to be improved, for example, the pigment described in Patent Document 1 is insufficient in light resistance, and the pigments described in Patent Documents 2 and 3 have a hue of green color and a low coloring power. Or shortcomings such as poor color characteristics. Further, Patent Documents 4 to 7 disclose dyes having excellent absorption properties and sufficient fastness. However, the specific compounds described in this patent document are poor in fastness even if they have a good hue, or are poor in hue even if they are good in fastness, and are easily dissolved in an organic solvent or water, or are resistant to chemicals (solvent resistance) Sexuality) is not sufficient. When using the three colors of yellow, magenta, and cyan, and the four colors of black, the color reduction method is used to express the full color, if only one pigment with poor fastness is used, the gray balance of the printed matter will be passed over time. When a change occurs, and if a pigment having a poor color characteristic is used, the color reproducibility at the time of printing is lowered. Therefore, in order to obtain a printed matter which maintains high color reproducibility for a long period of time, pigments and pigment dispersions in which color characteristics and fastness are desired are desired. In the past, azo dyes have various kinds of visible light absorption, and are used as pigments in various fields, such as coloring of synthetic resins, printing inks, dyes for sublimation-type thermal transfer materials, inks for inkjet, and color filters. It is used in various fields such as pigments. The large performance required for the azo dye as a pigment is an absorption spectrum. The hue of the pigment has a large effect on the color and feel of the object, which is colored by the pigment, and gives a visual effect. Therefore, research on the absorption spectrum of pigments has been conducted since ancient times. An azo dye having a nitrogen-containing five-membered ring as an azo component is known in the prior art, and is also disclosed in Patent Documents 8 to 9. Further, Patent Document 1 discloses a naphthol-based azo pigment in which a benzene ring and a naphthalene ring are bonded via an azo group. CITATION LIST PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT PATENT DOCUMENT Patent Document 5: International Publication No. 00/023525, Patent Document 6: JP-A-2008-1 3472, Patent Document 7: Japanese Patent Publication No. Hei 9-511278, Patent Document 8: Japanese Special Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. No. 2004-123866. An object of the present invention is to provide an azo compound, an azo pigment, an azo pigment dispersion, and a coloring composition which are excellent in coloring power and color, and excellent in fastness (especially solvent resistance). In the second aspect, an object of the present invention is to provide an azo compound, an azo pigment, an azo liquid dispersion, and a coloring composition which are excellent in light resistance. -7- 201033292 Further, an object of the present invention is to produce the azo pigment of the present invention or a tautomer thereof with good reproducibility and high efficiency. Means for Solving the Problems The inventors of the present invention repeated intensive studies and found that nitrogen-containing heterocyclic azo pigments having a specific structure and having characteristic X-ray diffraction peaks at specific positions in the first aspect or their mutual The isomers have good coloring power and hue, and exert good fastness (especially solvent resistance). Further, it has been found that a method for efficiently producing such a nitrogen-containing heterocyclic azo pigment or its hydrazine tautomer is finally completed. The inventors of the present invention have repeatedly conducted intensive studies, and as a result, found that the azo pigment having a characteristic X-ray diffraction peak at a specific position in the second aspect is excellent in hue, good in coloring power, and particularly excellent in light resistance. Further, for example, a coloring composition in which a pigment is dispersed, for example, a high-intensity optical density or the like can be produced even when printing at a high speed by inkjet or the like, and an inkjet recording ink having particularly excellent coloration can be produced. That is, the present invention is as follows: 偶[1] An azo pigment represented by the following formula (1), a tautomer, a salt, a hydrate or a solvate thereof, which is obtained by X-ray winding in a CuK α characteristic The Bragg angle of the shot (20 ± 〇.5.) is 7.1. 25.3°, 26.0. And 27.2. The characteristic X-ray diffraction peak is represented by the following formula (1).

201033292 [2] An azo pigment, a tautomer, a salt, a hydrate or a solvate thereof having a Bragg angle (20 ± 〇. 5 °) of a CuK α characteristic X-ray diffraction of 7.1. , η.7. 20.0. And 27.1° characteristic X-ray diffraction peaks are represented by the following formula (1).

[3] A method for producing an azo pigment or a tautomer thereof represented by the following formula (1), which comprises a diazo salt derived from a heterocyclic amine represented by the following formula (2) The compound represented by the following formula (3) is subjected to an azo coupling reaction step.

[4] The method for producing an azo pigment or a tautomer thereof according to [3], which comprises supplying the above formula (1) to a drying step and a post-treatment step "[5] as described in [4] A process for producing a nitrogen pigment or a tautomer thereof, wherein the aforementioned post-treatment step comprises heat treatment with a solvent having a solvent of SP to 7.0 to 14.0. [6] The method for producing an azo pigment or a tautomer thereof according to any one of [3] to [5] wherein the azo pigment represented by the above formula (1) is in CuKo: characteristic X-ray diffraction The angle of Prague (20 ± 〇. 5) is 7.1. 25.3. 26.0. And 201033292 27.2. Characteristic X-ray diffraction peaks. [7] The method for producing an azo pigment or a tautomer thereof according to [3], which comprises subjecting the above formula (1) to a post-treatment step in the presence of water. [8] The method for producing an azo pigment or a tautomer thereof according to [7] wherein the aforementioned post-treatment step comprises heat treatment with a solvent of a solvent having a SP値 of 7.0 to 14.0. [9] The method for producing an azo pigment or a tautomer thereof according to any one of [3], [7], or [8] wherein the azo pigment represented by the above formula (1) is in CuK α © The Bragg angle (20 ± 〇 · 5 °) of the characteristic X-ray diffraction is 7_1 °, 11.7 °, 20.0. And 27.1. Characteristic X-ray diffraction peaks. [10] A pigment dispersion characterized by containing the azo pigment, tautomer, salt, hydrate or solvate thereof according to any one of Π] to [9]. The article characterized by containing the pigment dispersion described in [10]. [12] An ink for inkjet recording, which comprises the composition of the color of [11]. [13] A coloring composition for a color filter, comprising the coloring composition according to [11]. [14] A color filter produced by using the coloring composition for a color filter according to [13]. EFFECTS OF THE INVENTION The azo pigment or tautomer thereof of the present invention is excellent in coloring power and color matching, and is excellent in fastness (especially solvent resistance). -10-201033292 Further, the pigment dispersion, the coloring composition, and the ink for inkjet recording of the present invention can be obtained by dispersing the azo pigment of the present invention in various media, and excellent in color characteristics, durability, and dispersion stability. . Further, according to the method for producing an azo pigment or a tautomer thereof of the present invention, the azo pigment of the present invention or a tautomer thereof can be produced with good reproducibility and high efficiency. [Embodiment] BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in detail below. The azo pigment of the first aspect of the present invention has a Bragg angle (20 ± 〇. 5 °) which is diffracted by a CuKa characteristic X ray of 7.1 ° and 25.3. ' 26.0. And 27.2. An azo pigment or a tautomer thereof having the characteristic X-ray diffraction peak represented by the following formula (1). The azo pigment of the second aspect of the present invention has a Bragg angle (2 〇.5°) which is diffracted by the X-ray of the CuKck characteristic, and is 7.1°, 11.7°, and 20.0. And 27.1. An azo pigment or a tautomer thereof having the characteristic X-ray diffraction peak represented by the following formula (1). In the present specification, the Bragg angle (2^0.5) of the X-ray diffraction of the CuK α characteristic is 7.1 ° and 25·3. 26.0° and 27.2. The azo pigment represented by the following formula having a characteristic X-ray diffraction peak is referred to as an α-type crystal form azo pigment. The Bragg angle (2M0.5) of the X-ray diffraction of the CuKa characteristic is 7.1. , 11.7. The azo pigments of the following formula (1) having characteristic X-ray diffraction peaks of 20.0° and 27.1° are referred to as self-type crystal form azo pigments. -11- 201033292 The azo pigments shown below can also be different crystalline polymorphs.

The pigment is a state in which the molecules are strongly bonded to each other by the cohesive energy of the strong interaction between the pigment molecules. In order to produce this state, it is necessary to use the van der Waals force and the intermolecular hydrogen bond between the molecules, for example, in the Japanese Society of Image Studies, Vol. 43, and page 10 (2 004). In order to enhance the inter-molecular van der Waals force, it is considered to introduce an aromatic group, a polar group, and/or a hetero atom into the molecule. Further, in order to form an intermolecular hydrogen bond, it is considered to introduce a substituent having a hydrogen atom bonded to a hetero atom and/or a substituent for introducing an electron donor into a molecule. Furthermore, it is considered that the higher the polarity of the entire molecule, the better. Therefore, for example, it is considered that the chain system such as an alkyl group is as short as possible, and the molecular weight/azo group is preferably smaller. According to these viewpoints, the pigment molecules generally preferably contain a guanamine bond, a sulfonamide bond, an ether bond, a seleno group, an oxycarbonyl group, an imido group, an amine mercapto fluorenyl group, a heterocyclic ring, a benzene group. The compound represented by the formula (1) is easy to form an intermolecular interaction of a dye molecule by a specific structure thereof, and has low solubility in water or an organic solvent, and can be used as an azo pigment. The pigment is different from the g-material which is dissolved in a molecularly dispersed state in water or an organic solvent, and is a fine dispersion of solid particles such as a molecular aggregate in a solvent. -12- 201033292 In the present invention, the X-ray diffraction measurement system of the α-type and A-type crystal form azo pigments represented by the above formula (1) can be in accordance with Japanese Industrial Standard JI SK 0 1 3 1 (X-ray diffraction) The general rule of analysis was carried out using a powder X-ray diffraction measuring apparatus RINT2500 (manufactured by Rigaku Co., Ltd.). In a single crystal form, the molecules become denser and the intermolecular interaction becomes stronger. As a result, solvent resistance, thermal stability, light resistance, gas resistance, print density increase, and the color reproduction range is expanded. Therefore, the azo pigment represented by the formula (1) and its tautomer are preferably 7.1 in the Bragg angle (26 > ± 0.5) of the CuKa characteristic X-ray diffraction 〇. 25.3. 26.0. And 27.2. Or 7.1 〇, 11.7 °, 20.0 °, and 27·1 ° have a characteristic crystalline form of the X-ray diffraction peak. Further, it is more preferably at 7.1 °, 10.7 °, and 14.5. 25.3. 26.0. And 27.2° or 7.1°, 8.7. , 11.7. , 20.0° and 27·1° have a characteristic X-ray diffraction peak crystal form. When the height of the peak at 27.2° of the Bragg angle (20±〇.5°) of the CuKa characteristic X-ray diffraction is 1, if the height of the peak at 20.0° is 0.2 or less, it is difficult to carry a yellow tone in the hue. It is better to look at it.

® Therefore, when at 27.2. When the height of the peak is 1, the height of the peak of 20.0° at the Brako angle of the characteristic X-ray diffraction (20±〇.5.) is preferably 0 to 0.2, more preferably 0 to 0·1, preferably For 〇~〇.〇5. When the CuKa characteristic is X-ray diffraction, the Bragg angle (2^±〇.5°) is 27.1. When the height of the peak is 1, it is at 25.3. The peak height is 〇.5 or less, and it is preferable from the viewpoint of further improving light resistance. So when at 27.1. When the height of the peak is 1, the Bragg angle (20.5) of the CuKa characteristic X-ray diffraction is 25.3. The height of the peak is preferably from 0 -13 to 201033292 to 0.5, more preferably from 0 to 0.3, and most preferably from 0 to 〇.2. When the primary particles of the azo pigment represented by the above formula (1) are observed by a transmission microscope, the length in the long axis direction is preferably O.Olym or more and 30#m or less, more preferably 〇_〇15//m or more. Below 〇em, it is particularly preferably O.〇2em or more and 0·5 m or less. Since the length in the long-axis direction when the primary particles are observed by the transmission microscope is 0.01/zm or more, the fastness to light or ozone and the dispersibility as a pigment dispersion can be more reliably exhibited. On the other hand, since the length in the longitudinal direction of the ytterbium is 30/m or less, when the desired volume average particle diameter is dispersed, it is less likely to become a super-dispersed state, and aggregation does not easily occur, so that the pigment dispersion can be more reliably exhibited. Preservation stability. When the length of the primary particle in the long-axis direction is within the above range, it exhibits high fastness to light or ozone, and the pigment dispersion is preferably excellent in storage stability. As described above, the azo pigment of the present invention exhibits excellent characteristics in coloring power and color characteristics by having a specific structure and having characteristic X-ray diffraction peaks at specific positions, and It also exhibits excellent properties in terms of fastness (especially solvent resistance). The scope of the present invention also encompasses the tautomer of the azo pigment represented by the formula (1). Formula (1) is represented by a limit structural formula among several tautomers which can be taken from a chemical structure, but may be a tautomer other than the structure described, or may be a complex number A mixture of tautomers is used. For example, among the pigments represented by the formula (1), -14-201033292 azo-oxime tautomers represented by the following formula (1) are considered. The range of the present invention also includes a compound represented by the following formula (1) in the tautomer of the azo pigment represented by the formula (1). The ratio of azo to hydrazine can be easily grasped semi-quantitatively by solid-state NMR measurement or Raman absorption measurement. Although both azo and hydrazine exert good performance, 'but from the viewpoint of hue, it is preferable that the ratio of bismuth is large. Preferably, 腙 is more than 50%, more preferably more than 80%, and most preferably more than 9%.

In particular, the Bragg angle (20 ± 〇. 5 °) of the X-ray diffraction of the CuK α characteristic was 7.1 °, 25.3. 26. And 27.2. The α-type crystalline form azo pigment represented by the following formula (1) having a characteristic ray-ray diffraction peak is characterized by good absorption characteristics of a red pigment, and is most suitable for photo-reproducibility of photo use and CF use. In the field. On the other hand, in the CuKo: characteristic X-ray diffraction Bragg angle (20 ± 〇.5.) is 7.1. , 11.7°, 20.0° and 27.1. The β-type crystalline form azo pigment represented by the following formula (1) having a characteristic X-ray diffraction peak is characterized by high light resistance display characteristics and is most suitable for the field of durability of a colored image. [Method for producing azo pigment or its tautomer] The azo pigment or its tautomer of the present invention is produced by the method of producing an azo pigment or a tautomer thereof represented by the following formula (1), The azo coupling reaction of the diazonium salt derived from the heterocyclic amine represented by the following formula (2) and the compound of -15 to 201033292 represented by the following formula (3) is carried out. This production method is a method for producing an azo pigment represented by the formula (1) or a tautomer thereof with good reproducibility and high efficiency.

The preparation of the diazo gun salt and the coupling reaction of the diazonium salt with the compound of the formula (3) can be carried out by conventional methods. The diazonium salt of the heterocyclic amine represented by the formula (2) is prepared, for example, in a reaction medium containing an acid such as hydrochloric acid, sulfuric acid, phosphoric acid, acetic acid, propionic acid, methanesulfonic acid, trifluoromethanesulfonic acid or the like. A conventional diazonium salt preparation method using a nitroxyl ion source such as nitrous acid, nitrite or nitrosyl sulfate is applicable. Examples of the more preferable acid include a case where acetic acid, propionic acid, methanesulfonic acid, phosphoric acid, or sulfuric acid is used alone or in combination, and more preferably phosphoric acid or acetic acid and sulfuric acid, acetic acid and c. Acidic hydrazine, acetic acid and propionic acid and sulfuric acid, particularly preferably phosphoric acid. As a preferred example of the reaction medium (solvent), an organic acid or an inorganic acid is preferably used, and particularly preferably phosphoric acid, sulfuric acid, acetic acid, propionic acid or methanesulfonic acid, of which phosphoric acid is preferred. Examples of preferred nitroxyl ion sources include nitrites, nitrites, and nitrosylsulfuric acid. More preferably, sodium nitrite, potassium nitrite, isoamyl nitrite, nitrosylsulfuric acid (for example, hydrazine NHS04 sulfuric acid solution), particularly by using sodium nitrite, can stably and efficiently modulate heavy-16 - 201033292 Nitrogen salt. In this case, a trapping agent (for example, urea) for trapping an excessive amount of a substance derived from sodium nitrite (for example, nitroxyl ion) may be appropriately added to the reaction medium, whereby the above excess amount may be suppressed. The formation of impurities caused by the substance. The solvent is preferably used in an amount of from 0.5 to 50 times by mass, more preferably from 1 to 20 parts by mass, particularly preferably from 3 to 15 parts by mass, based on the heterocyclic amine of the formula (2). In the present invention, the heterocyclic amine of the formula (2) may be in a state of being dispersed in a solvent, or may be in a state of being a solution depending on the type of the diazo component, and is preferably a solution. status. The amount of the nitroxyl ion source to be used is preferably from 0.95 to 5.0 equivalents, more preferably from 1.00 to 3 to 00 equivalents, particularly preferably from 1,000 to 1.50 equivalents, based on the heterocyclic amine of the formula (2). The reaction temperature is preferably from -15 ° C to 40 ° C, more preferably from - l ° ° C to 35 ° C ', more preferably from -5 ° C to 30 ° C. If it is lower than -1 5 °C, the reaction rate is remarkably slowed, and the time required for the synthesis becomes significantly longer, so it is not economical. If the synthesis is carried out at a high temperature exceeding 40 ° C, the amount of by-product formation increases. Not suitable. The reaction time is preferably from 30 minutes to 300 minutes, particularly preferably from 30 minutes to 200 minutes, more preferably from 30 minutes to 150 minutes. The compound represented by the formula (3) can also be obtained from a commercially available product, which can be produced by the method described in JP-A-2008-136472. [Coupling reaction step] The coupling reaction step can be carried out in an acidic reaction medium to an alkaline reaction medium, but the azo pigment of the present invention is preferably carried out in an acidic to neutral reaction medium to inhibit diazo salt. Decomposed and efficiently derivatized into azo-17-201033292 pigment. As a preferred example of the reaction medium (solvent), an organic solvent, particularly preferably an organic solvent, is preferably used, and a solvent which exhibits a uniform solution with a solvent in a reverse separation phenomenon is preferred. Ketone diol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol, such as methanol, ethanol, propanol, isopropanol, butanol, butanol organic solvent, acetone, methyl ethyl ketone, etc. a glycol-based organic solvent such as an diol-based organic solvent, ethylene glycol monomethyl ether ether or ethylene glycol diethyl ether, decane or acetonitrile, etc., and these solvents may be two or more types. The organic solvent having a polar parameter (ET) of 40 or more is preferably an alcohol solvent having three or more diol atoms having two or more hydroxyl groups in a solvent molecule, and preferably having a total carbon number of 5 or less and having a carbon number of 2 or less. An alcohol solvent (for example, a ketone solvent having a methanol carbon number of 4 or less (for example, acetone or methyl ethyl group contains a mixed solvent of the above). Further, as a preferred example of the reaction medium, a protic solvent may also be used as the polar non-polar solvent. Examples of protic solvents, 1 methylformamide, hydrazine, hydrazine-dimethylacetamide, N-methyl-2. hydrazine, tetramethylurea, acetone, methyl ethyl ketone, acetyl Solvents, etc. Among these solvents, acetone, hydrazine, hydrazine dimethyl dimethyl acetamide, acetonitrile are particularly preferred. In the present invention, the compound represented by the formula (3) may be an organic acid in which an organic acid or a pentanol may be used as an extension acid or an inorganic acid. , a mixture of ethylene glycol, 1,3-propane, ethylene glycol monoethyltetrahydrofuran, and a mixture of two ij. A solvent, wherein a solvent or a ketone solvent of carbon, ethylene glycol) or total ketone ketone). Further, the polarity is not limited to N,N-di-pyrrolidone, dinitrile, and such mixed methyl ethyl ketone, and the -18-201033292 state in the solvent of the above formula (3) 'It can also be the state of the solution, either state. Further, the reaction medium exemplified above may contain an acid-containing reaction medium used for derivatizing a heterocyclic amine which is not represented by the formula (2) into a diazo salt. The amount of the solvent to be used is preferably from 1 to 1 (by mass) times the compound represented by the above formula (3), more preferably from 1 to 50 times by mass, still more preferably from 2 to 30 times by mass. The amount of the compound represented by the formula (3) is preferably from 0.5 to 5 equivalents, more preferably from 0.6 to 3 equivalents, particularly preferably from 6 to 1.5 equivalents, based on the diazo salt. ® reaction temperature is preferably -3 (TC ~ 30 ° C, especially preferably -20 ° C ~ 20 ° C 'better than - lot ~ lot. If below -30 Ό, the reaction rate is significantly slower' synthesis The time required is significantly longer, so it is uneconomical, and if the synthesis is carried out at a high temperature exceeding 30 ° C, it is not preferable because the amount of by-product formation is increased. The reaction time is preferably from 30 minutes to 300 minutes, and particularly preferably 30 minutes to 250 minutes, more preferably 30 minutes to 200 minutes. In the synthesis method of the azo pigment or its tautomer of the present invention, the product obtained by the reaction (crude azo pigment) is After the treatment is carried out according to the usual treatment method after the organic synthesis reaction, it can be supplied with or without purification. That is, for example, it may be purified from the reaction system or may be recrystallized or salted separately or in combination. Further, after the completion of the reaction, the reaction solvent may be distilled off, or may be poured into water or ice without being distilled, neutralized or not neutralized, and the free or organic solvent/aqueous solution may be used. Extracted, not refined or performed separately or in combination It is supplied by a refining operation such as recrystallization, crystallization, or salt formation. -19- 201033292 A method for synthesizing the azo pigment of the present invention or a tautomer thereof will be described in more detail. The azo pigment of the present invention or The method for producing a tautomer is preferably a coupling reaction of a diazo compound which is diazolized with a heterocyclic amine represented by the above formula (2) and a compound represented by the above formula (3). The compound represented by the formula (3) is dissolved in an organic solvent to carry out a coupling reaction. The diazolization reaction of the heterocyclic amine represented by the above formula (2) can be carried out, for example, by an acidic solvent such as sulfuric acid, phosphoric acid or acetic acid. In the middle, the reagent such as sodium nitrite or sulfonium nitrosulfuric acid is reacted at a temperature of 30 ° C or lower for 10 minutes to 6 hours. The coupling reaction is preferably a diazo salt obtained by the above method. The compound represented by the above formula (3) is reacted at 40 ° C or lower, preferably at 20 ° C or lower for 10 minutes to 12 hours. As a method for producing an azo pigment, for example, it is preferably used in the above formula ( 3) The compound shown is once dissolved in an organic solvent and then subjected to The method of the present invention in which the reaction is carried out. Examples of the organic solvent which can be used in this case include an alcohol solvent, a ketone solvent, and a polar aprotic solvent. Examples of the alcohol solvent are preferably methanol, ethanol or isopropyl alcohol. An alcohol, ethylene glycol, diethylene glycol, etc., and particularly preferably methanol. As an example of the ketone solvent, acetone, methyl ethyl ketone, cyclohexanone, etc. are preferable, and among them, acetone is particularly preferred. Examples of the protic solvent 'In addition to acetone and methyl ethyl ketone exemplified as the ketone solvent, N,N-dimethylformamide, N,N-dimethylacetamide, N- are preferred. Methyl-2-pyrrolidone, dimethyl sulfite, tetramethyl urea, acetonitrile, etc., particularly preferably hydrazine, hydrazine dimethyl acetamide. The azo pigment or its tautomerism as described above In the preparation method of the present invention, -20-201033292 is particularly preferably a heterocyclic amine represented by the formula (2), and a diazo key derived from the heterocyclic amine is prepared by using a solution in which the heterocyclic amine is dissolved in phosphoric acid. a solution of the salt, followed by dissolving the solution of the above diazonium salt and the compound represented by the above formula (3) in N, N-di Group as acetamide was carried out the azo coupling reaction. In the above preferred embodiment, the reaction medium for the coupling reaction step, in addition to N,N-dimethylacetamide, can also be used for diazotization of phosphoric acid as the heterocyclic amine represented by formula (2). The state of the acid-containing reaction medium. Further, phosphoric acid used for derivatizing a heterocyclic amine represented by the formula (2) into a diazo salt is a function of an acid and a reaction medium in the above acid-containing reaction medium. The compound obtained by the above production method can be supplied to the purification step depending on the use. As a purification step, a base may be added to adjust the pH. When the pH is adjusted, the pH is preferably 4 to 10», wherein the pH is more preferably 5 to 8, and particularly preferably 5.5 to 7.5. If the pH is 10 or less, the hue does not increase the yellow tone, and the hue is ϋW. The point of view is better. When the pH is 4 or more, for example, when it is used as an ink for inkjet recording, it is preferable that problems such as corrosion of the nozzle are less likely to occur. In the production method of the present invention, the above formula (1) is preferably supplied to the drying step and the post-treatment step. Thereby, an azo pigment 良好 having a good purity can be obtained. [Post-Processing Step] The compound represented by the formula (1) of the present invention is preferably subjected to solvent heat treatment as a post-treatment step. Thereby, an α-crystal form of -21-201033292 azo pigment of good purity can be obtained. In the present invention, the post-treatment step preferably comprises heat treatment with a solvent of a solvent having an SP値 of 7.0 to 14.0. The impurities in the pigment can be removed by heating with the solvent. As the solvent for the solvent heat treatment, a solvent having a SP 値 of 7.0 to 14.0 is preferably used, and SP 値 is preferably 9.0 to 13.0, more preferably ethyl acetate, dibutyl phthalate, acetone, or isopropanol. , acetonitrile, acetic acid, hydrazine, hydrazine-dimethylacetamide, hydrazine, hydrazine-dimethylformamide, preferably using acetone, acetonitrile, hydrazine, hydrazine dimethyl acetamide, hydrazine, hydrazine - Dimethylformamide. The amount of the solvent used for the solvent heat treatment differs depending on the kind of the solvent, but is preferably from 1 to 100 times by weight, more preferably from 5 to 70 times by weight, more preferably from 5 to 70 times by weight, more preferably 5 parts by weight of the compound represented by the formula (1). ~30 times the weight. Further, an inorganic or organic acid or a base may be added to the above-mentioned solvent. The temperature of the solvent heat treatment varies depending on the primary particle size of the desired pigment, and is preferably from 40 to 150 ° C, more preferably from 60 to 10 (TC. Further, the treatment time is preferably 3 0 minutes to 2 hours. The above-mentioned tautomerism and control of the crystal polymorph can be controlled by the production conditions at the time of post-treatment. Examples of the post-treatment include solvent salt milling, salt milling, and dry milling. The pigment particle control step such as solvent honing, acid paste or the like, and a pigment particle control step, such as a resin, a surfactant, a dispersant, etc. The solvent salt mill may, for example, be coarse. The azo pigment, the inorganic salt, and the organic solvent insoluble therein are put into a kneader and kneaded and ground therein. As the above inorganic salt, a water-soluble inorganic salt can be suitably used, for example, it is preferably used in -22-201033292. An inorganic salt such as sodium chloride, potassium chloride or sodium sulfate. Further, an inorganic salt having an average particle diameter of 0.5 to 50/zm is more preferably used. The amount of the inorganic salt used is preferably relative to the crude azo pigment. 3 to 20 times the mass, more preferably 5 to 15 times the mass. In the organic solvent, a water-soluble organic solvent can be suitably used, and the solvent is easily evaporated due to an increase in temperature during kneading. Therefore, from the viewpoint of safety, a solvent having a high boiling point is preferred. Examples thereof include diethylene glycol, glycerin, ethylene glycol, propylene glycol, liquid polyethylene glycol, liquid polypropylene glycol, 2-(methoxymethoxy)ethanol hydrazine, 2-butoxyethanol, and 2- (isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, three Ethylene glycol monomethyl ether, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol or The mixture of the water-soluble organic solvent is preferably 0.1 to 5 times by mass relative to the crude azo pigment. The kneading temperature is preferably 20 to 130 ° C, particularly preferably 40 to 110 °. C. Examples of the kneader include a kneader, a mixing honing machine, etc. ® [Drying step] In the production method of the present invention, the above formula 1) It can be supplied to the drying step as needed. The compound represented by the formula (1) is preferably neutralized after the azo coupling reaction, and the powder obtained by filtration or the like is further dried before being supplied to the solvent for heat treatment. Further, the compound is obtained, whereby the α-type crystal form azo pigment can be produced with better reproducibility and higher efficiency. Further, the compound is preferably used in a blow dryer at 1 hour and 50° (: In the case of the weight -23-201033292, the change is 20% or less, and it is sufficiently dried. It is preferable to use a blower dryer at a temperature of 1 hour or 50. (:: the weight change by drying is 10% or less, more preferably 5% or less, particularly preferably 1% or less. The smaller the weight change, the more the amount of solvent used for the heat treatment can be reduced. [Processing step after coexistence of water] In another aspect of the invention, the above formula (1) is preferably subjected to a post-treatment step in the presence of water. Thereby, the /S type crystal form azo pigment can be produced with better reproducibility and higher efficiency. As a post-treatment step, it is preferred to carry out the aforementioned solvent heat treatment. The compound of the formula (1) which is supplied to the solvent heat treatment is preferably a compound which is neutralized by a powder obtained by filtration or the like after the azo coupling reaction, and which has been subjected to a filtration step. The water content of the compound in the presence of water is preferably 100% by weight or more, more preferably 200% or more, and particularly preferably 500% or more, by weight change. 〇 [Pigment Dispersion] The pigment dispersion of the present invention is characterized by containing an α-form crystal form azo pigment or a tautomer thereof, or an azo pigment or a tautomer thereof obtained by the process of the present invention. This makes it possible to obtain a pigment dispersion excellent in color characteristics and dispersion stability. Further, another aspect of the pigment dispersion of the present invention is characterized by containing an azo-type crystal form azo pigment or a tautomer thereof, or an azo pigment or a tautomer thereof obtained by the process of the present invention. Thereby, it is possible to obtain a pigment dispersion excellent in durability and dispersion stability. The pigment dispersion of the present invention may be aqueous or non-aqueous, and is preferably a water-based pigment dispersion. In the aqueous pigment dispersion of the present invention, the aqueous liquid system for dispersing the pigment may be a mixture containing water as a main component and a hydrophilic organic solvent as desired. Examples of the hydrophilic organic solvent include methanol, ethanol, propanol, isopropanol, butanol, isobutanol, second butanol, third butanol, pentanol, hexanol, cyclohexanol, and benzene. Alcohols such as methanol, ethylene glycol, diethylene glycol oxime, triethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, polypropylene glycol, butanediol, hexanediol, pentanediol, glycerol, Polyols such as hexanetriol and thiodiglycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol Alcohol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monobutyl ether, dipropylene glycol monomethyl ether, triethylene glycol monomethyl ether, ethylene glycol diacetate, ethylene glycol monomethyl acetate a glycol derivative such as triethylene glycol monoethyl ether or ethylene glycol monophenyl ether; ethanolamine, diethanolamine, triethanolamine, N-methyldiethanolamine, N-ethylguanidinoethanolamine, morpholine, Amines such as N-ethylmorpholine, ethylenediamine, diethylenetriamine, triamethylenetetramine, polyethyleneimine, tetramethylpropanediamine, formazan, N,N-dimethyl Amine, N,N-dimethylacetamide, dimethyl hydrazine, Cyclobutane, 2-pyrrolidone, N-methylpyrrolidone, N-ethyl sulphate 2, 曙 曙 酮 ketone, I, 3 - dimethyl 2 - oxalinone, acetonitrile, acetone, and the like. Further, the aqueous pigment dispersion of the present invention may further contain an aqueous resin. Examples of the aqueous resin include a water-soluble resin dissolved in water, a water-dispersible resin dispersed in water of -25 to 201033292, a colloidal dispersion resin, or a mixture thereof. Specific examples of the aqueous resin include acrylic, styrene-acrylic, polyester, polyamine, polyurethane, and fluorine resins. The aqueous pigment dispersion of the present invention contains water. When the resin is used, the content thereof is not particularly limited. For example, it may be 〇~1 〇 〇 mass% with respect to the pigment. Further, in order to improve the dispersion of the pigment and the quality of the image, a surfactant and a dispersant may also be used. The surfactant may, for example, be an anionic, nonionic, cationic or ionic surfactant. Any surfactant may be used, and an anionic or nonionic surfactant is preferably used. When the aqueous pigment dispersion of the present invention contains a surfactant, the content thereof is not particularly limited. For example, it may be from 〜 to 100% by mass based on the pigment. Examples of the anionic surfactant include a fatty acid salt, an alkyl sulfate salt, an alkylbenzenesulfonate, an alkylnaphthalenesulfonate, a dialkyl sulfosuccinate, and an alkyl diaryl ether. Sulfonate, alkyl phosphate, polyoxyethylene alkyl ether sulfate, polyoxyethylene alkyl aryl ether sulfate, naphthalenesulfonic acid formalin condensate, polyoxyethylene alkyl phosphate salt, glycerol borate Fatty acid esters, polyoxyethylene glycerin fatty acid esters, and the like. Examples of the nonionic surfactant include polyoxyethylene alkyl ether, polyoxyethylene alkyl aryl ether, polyoxyethylene propylene oxide block copolymer, sorbitan fatty acid ester, and polyoxyethylene sorbent pear. Sugar alcohol ester grease-26- 201033292 Fatty acid ester, polyoxyethylene sorbitan fatty acid ester, glycerin fatty acid ester, polyoxyethylene fatty acid ester, polyoxyethylene alkylamine, fluorine, lanthanide, etc.

Q The non-aqueous pigment dispersion of the present invention is obtained by dispersing the pigment represented by the above formula (1) in a non-aqueous medium. The resin used in the non-aqueous vehicle liquid can be, for example, petroleum resin, casein, shellac, rosin-modified maleic acid resin, rosin-modified phenol resin, nitrocellulose, cellulose acetate butyrate, cyclized rubber. , chlorinated rubber, oxidized rubber, hydrochloric acid rubber, phenol resin, alkyd resin, polyester resin, unsaturated polyester resin, amine resin, epoxy resin, vinyl resin, vinyl chloride, vinyl chloride-vinyl acetate Copolymer, acrylic resin, methacrylic resin, polyurethane resin, enamel resin, fluororesin, drying oil, synthetic drying oil, styrene/maleic acid resin, styrene/acrylic resin, polyamide resin, Polyimine resin, benzoguanamine resin, melamine resin, urea resin chlorinated polypropylene, butyral resin, vinylidene chloride resin, and the like. As the nonaqueous vehicle, a photocurable resin can also be used. In addition, examples of the solvent to be used for the nonaqueous vehicle include an aromatic solvent such as toluene stomach, xylene or methoxybenzene, ethyl acetate or butyl acetate, propylene glycol monomethyl ether acetate, and propylene glycol. An acetate solvent such as monoethyl ether acetate or a propionate solvent such as ethoxyethyl propionate; an alcohol solvent such as methanol or ethanol; butyl cellosolve; propylene glycol monomethyl ether; An ether solvent such as an alcohol ethyl ether or diethylene glycol dimethyl ether; a ketone solvent such as methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone; or an aliphatic hydrocarbon solvent such as hexane , N,N-dimethylformamide, r-butyrolactam, N-methyl-2-pyrrolidone, aniline, pyridine, etc., nitrogen compound solvent, r-butyl -27-201033292 lactone, etc. A lactone-based solvent, a urethane such as a mixture of methyl carbamate and ethyl urethane of 48:52, and the like. In the present invention, the volume average particle diameter of the pigment particles is preferably not more than 10 nm and not more than 250 nm. Further, the volume average particle diameter of the pigment particles means the particle diameter of the pigment itself, or when the additive such as a dispersant adheres to the pigment, the particle diameter to which the additive is attached. In the present invention, a device for measuring the volume average particle diameter of the pigment particles can be a Nanotrac UPA particle size analyzer (UPA-EX150: manufactured by Nikkiso Co., Ltd.). In the measurement, 3 ml of the pigment dispersion was placed in a measuring cartridge and carried out in accordance with the specified measuring method. Further, as an input parameter of the measurement, the viscosity is the ink viscosity, and the density of the dispersed particles is the density of the pigment. More preferably, the volume average particle diameter is from 10 nm to 250 nm, more preferably from 20 nm to 230 nm. When the number average particle diameter of the particles in the pigment dispersion is less than 1 Onm, the storage stability may not be ensured. On the other hand, when the number exceeds 250 nm, the optical density may be lowered. The concentration of the pigment contained in the pigment dispersion of the present invention is preferably in the range of from 1 to 35 mass%, more preferably from 2 to 25 mass%. If the concentration is less than 1% by mass, a sufficient image density will not be obtained when the pigment dispersion is used alone as an ink. When the concentration exceeds 35% by mass, the dispersion stability is lowered. The pigment dispersion of the present invention can be obtained by dispersing the above azo pigment and an aqueous or nonaqueous medium using a dispersing device. As a dispersing device, a simple agitator or impeller stirring method, in-line stirring method, and honing method (for example, a colloid mill, a ball mill, a sand mill, a bead mill, a vertical ball mill -28-201033292, a roller mill can be used. Machine, jet mill, paint mixer, mixing honing machine, etc.), ultrasonic method, high pressure emulsification dispersion method (high pressure homogenizer; specific commercial equipment is Gaulin homogenizer, microfluidizer bed, DeBEE2〇〇0 Wait). Examples of the use of the azo pigment of the present invention include image recording materials for forming an image, particularly a color image, specifically, an ink jet recording material as described in detail below, and a thermal recording material and a pressure sensitive recording. Materials, electrophotographic recording materials, transfer silver halide photosensitive materials, printing inks, gS recording pens, etc., preferably ink jet recording materials, thermal recording materials, and electrophotographic recording materials, More preferably, it is an inkjet recording material, and can be applied to a solid-state imaging device such as a CCD or a color filter for recording and reproducing a color image used for a display such as an LCD or a PDP, or a dyeing liquid for dyeing various fibers. . The azo pigment of the present invention can be used by adjusting the physical properties such as solvent resistance, dispersibility, and heat transfer property suitable for the purpose of the use. Further, the azo pigment of the present invention can be used in an emulsified dispersion state according to the system used, and can be used even in a solid dispersion state. [Coloring composition] The coloring composition of the present invention means a coloring composition containing the above azo pigment or its tautomeric isomer or the above pigment dispersion. The coloring composition of the present invention may contain a medium, but is particularly suitable as an ink for inkjet recording when a solvent is used as the medium. The coloring composition of the present invention can be produced by dispersing the azo pigment of the present invention in a medium using a lipophilic medium or an aqueous medium as a medium. It is preferred to use an aqueous medium. -29- 201033292 In the coloring composition of the present invention, an ink composition for removing the medium is also included. The coloring composition of the present invention may contain other additives as needed within the range not impairing the effects of the present invention. Examples of other additives include anti-drying agents (wetting agents), anti-fading agents, emulsion stabilizers, penetration enhancers, ultraviolet absorbers, preservatives, mold inhibitors, pH adjusters, surface tension adjusters, and defoaming agents. A well-known additive such as a solvent, a viscosity modifier, a dispersing agent, a dispersion stabilizer, a rust preventive, and a chelating agent is described in JP-A-2002-306623. In the case of water soluble inks, these various additives are added directly to the ink. In the case of oil-soluble inks, it is generally added to the dispersion after the preparation of the azo pigment dispersion, but it may also be added to the oil phase or the aqueous phase during the preparation. [Inkjet for Inkjet Recording] Next, the ink for inkjet recording of the present invention will be described. The ink for inkjet recording of the present invention (hereinafter also referred to as "ink") is a pigment dispersion of the present invention described above. It is preferably prepared by mixing a water-soluble solvent, water or the like. However, the pigment dispersion of the present invention described above can be used as it is without any particular problem. The content ratio of the pigment dispersion in the ink of the present invention is preferably in the range of 1 to 100% by mass in consideration of the hue, color density, chroma, transparency, etc. of the image formed on the recording medium. It is particularly preferably in the range of 3 to 20% by mass, and most preferably in the range of 3 to 10% by mass. In the ink of 100 parts by mass of the ink of the present invention, it is preferable to contain 0.1 part by mass or more and 20 parts by mass or less of the pigment of the present invention, and more preferably 0.2 part by mass or more and 10 parts by mass or less, more preferably 1 to 10 parts by mass. . Further, in the ink of the present invention, in -30-201033292, other pigments may be used together with the pigment of the present invention. When two or more types of pigments are used, the total content of the pigments is preferably in the above range. The ink of the present invention can be used not only for image formation in monochrome but also for full color image formation. In order to form a full-color image, red, ink, and yellow inks can be supplied, and in order to adjust the color tone, black ink can be used. Further, in addition to the use of the azo pigment of the present invention described above, the ink of the present invention may simultaneously use other pigments. Examples of applicable yellow pigments include CIPY74, CIpY i28, CIPY155, and CIPY213', which are applicable magenta pigments, and examples thereof include CIPV19 and CIPR122, and examples of suitable cyan pigments include ί:·Ι·Ρ·Β·15:3, (:·Ι·Ρ·:Β.15:4, any of these can be used separately. As an applicable black material, bisazo, A dispersion of a trisazo, a tetrazo pigment, and a carbon black. The water-soluble solvent used in the ink for inkjet recording of the present invention is a polyhydric alcohol, a polyhydric alcohol derivative, a nitrogen-containing solvent, an alcohol, or the like. Sulfur solvent, etc. As a specific example, ethylene glycol, diethylene glycol, propylene glycol, butanediol, triethylene glycol, 15-pentanediol, 1,2,6-hexanetriol, etc. are mentioned as a polyhydric alcohol. Glycerol, etc. Examples of the polyhydric alcohol derivative include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, and Ethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monobutyl ether, dipropylene glycol monobutyl ether, diglycerin Further, as the nitrogen-containing solvent, pyrrolidone, N-methyl-2-pyrrolidone, cyclohexylpyrrolidone, triethanolamine, etc. may be mentioned as the ethylene oxide adduct. Examples of the alcohols include alcohols such as ethanol, isopropyl alcohol, butanol, and benzyl alcohol. Examples of the sulfur-containing solvent include sulfur diethanol, thiodiglycerol, cyclobutyl hydrazine, and dimethyl hydrazine. The water-soluble solvent used in the present invention may be used singly or in combination of two or more kinds. The content of the water-soluble solvent is 1% by mass of the entire ink. It is used in an amount of 60% by mass or less, preferably 5% by mass or more and 40% by mass or less. When the amount of the water-soluble solvent in the ink is less than 1% by mass, a sufficient optical density may not be obtained. On the other hand, if it is more than 60% by mass, the viscosity of the liquid becomes large, and the ejection characteristics of the ink liquid may become unstable. The preferred physical properties of the ink for inkjet recording of the present invention are as follows. The tension is preferably 20 mN/m or more and 60 mN/m or less, and particularly preferably 2 0 mN or more and 45 mN/m or less, more preferably 25 mN/m or more and 35 mN/m or less. When the surface tension is less than 20 mN/m, the nozzle surface of the recording head overflows with liquid, and the printing cannot be performed normally. On the other hand, when it exceeds 60 mN/m, the permeability to the recording medium after printing becomes slow, and the drying time becomes slow. Further, the surface tension is the same as described above using a Wilhelmy type surface tension meter at 23°. The viscosity of the ink of the ink is preferably 1.2 mPa_s or more and S.OmPa.s or less, and more preferably 1.5 mPa*s or more and less than 6.0 mPa·s, more preferably 1.8 mPa.s. -32- 201033292 Above and below 4.5mPa, s. When the viscosity is more than 8.0 mPa·s, the spit property is lowered. On the other hand, when it is smaller than UmPa.s, the long-term ejection property is deteriorated. In addition, the measurement of the viscosity (including the following) was carried out using a rotary viscometer Rheomat 115 (manufactured by Contraves Co., Ltd.) at a shear rate of 23 ° C of 1 400 s·1. In the ink, water is added in addition to the above components to achieve the above preferred range of surface tension and viscosity. The amount of water added is not particularly limited, and is preferably 1% by mass or more and 99% by mass or less, more preferably 30% by mass or more and 80% by mass or less based on the total amount of the ink. In addition, polyethyleneimine, polyamine, polyvinylpyrrolidone, polyethylene glycol, ethyl cellulose, carboxymethyl cellulose, etc. may be used for the purpose of controlling the characteristics such as improvement in spoutability. Cellulose derivatives, polysaccharides and derivatives thereof, other water-soluble polymers, acrylic polymer emulsions, polyurethane emulsions, polymer emulsions such as hydrophilic latex, hydrophilic polymer gels, rings Dextrin, macrocyclic amines, dendrimers, crown ethers, urea and its derivatives, acetamide, polyoxo-based surfactants, fluorine-based surfactants, and the like. Further, in order to adjust the conductivity and pH, an alkali metal compound such as potassium hydroxide, sodium hydroxide or lithium hydroxide, ammonium hydroxide, triethanolamine, diethanolamine, ethanolamine or 2-amino-2-methyl can be used. A nitrogen-containing compound such as -1-propanol or an alkaline earth metal compound such as calcium hydroxide; an acid such as sulfuric acid, hydrochloric acid or nitric acid; a salt of a strong acid such as ammonium sulfate or a weak base; Further, a pH buffer, an antioxidant, a mold inhibitor, a viscosity adjuster, a conductive agent, an ultraviolet absorber, or the like may be added as needed. -33-201033292 [Coloring composition for color filter] The coloring composition for a color filter of the present invention contains the above-described pigment composition of the present invention, and more preferably contains a polymerizable compound and a solvent. Further, when the coloring composition for a color filter of the present invention is produced, the azo pigment obtained as described above may be blended as it is, or a pigment dispersion which has been dispersed in a solvent may be blended. It is preferred that the azo pigment is a pigment dispersion and is excellent in color characteristics, durability, dispersion stability, light resistance or weather resistance. The amount of the organic pigment to be used in the coloring composition of the color filter of the present invention is preferably 0.01 to 2 parts by mass, particularly preferably 0.1 to 1 part by mass, per part by mass of the polymerizable compound. [Polymerizable compound] The polymerizable compound can be suitably selected in consideration of the process of the color filter. Examples of the polymerizable compound include a photosensitive compound and/or a thermosetting compound, and particularly preferably a photosensitive compound. The photosensitive compound is preferably one having an ethylenically unsaturated bond selected from at least one of a photopolymerizable resin, a photopolymerizable monomer, and a photopolymerizable oligomer. In the colored composition for a color filter, a resin which is in a cured state may be contained, and a component which is not resinized may be contained in an unhardened state. Examples of the photopolymerizable compound, the photopolymerizable monomer, and the photopolymerizable oligomer include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, and (meth)acrylic acid. 2-ethylhexyl ester, ethylene glycol di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(methyl)propyl-34-201033292 enoate, polyethyl b Diol di(meth)acrylate, pentaerythritol di(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A epoxy di(methyl) (meth)acrylates such as acrylate, bisphenol F-type epoxy di(meth)acrylate, bisphenolphthalein epoxy di(meth)acrylate, and the like. Further, a vinyl resin such as an acrylic (co)polymer, a (meth)acrylic (co)polymer or a maleic acid (co)polymer, or polyethylene oxide or polyvinylpyrrolidone may be mentioned. , Polyamide, polyurethane, polyether, polyester, etc., which have an ethylenic double bond in the side chain. These may be used singly or in combination of two or more. The blending amount of the polymerizable compound may be in the range of 20 to 95% by mass, preferably 40 to 80% by mass based on the total solid content of the color filter composition. The blending ratio of the polymerizable compound is preferably from 40 to 95% by mass, more preferably from 50 to 90% by mass, based on the total solid content of the color filter composition. In the composition, other resins or the like may be blended as needed. In this case, the total amount of other resins is preferably within the above range. In addition, all the solid components are components which remain as a solid component after drying and hardening, and Θ do not contain a solvent, but contain a monomer. [Photopolymerization Initiator] When a photosensitive compound is used as the polymerizable compound, a photopolymerization initiator is used together with the monomer and/or oligomer of the photosensitive compound. Examples of the photopolymerization initiator include a benzophenone derivative, an acetophenone derivative, a benzoin derivative, a benzoin ether derivative, a thioxanthone derivative, an anthracene derivative, and a naphthoquinone derivative. One or more selected from the compounds such as the compound and the tri-negative derivative. Along with this photopolymerization initiator, a well-known light sensitization -35-201033292 agent can be used. Examples of the thermosetting resin' include melamine resin, urea resin, alkyd resin, epoxy resin, phenol resin, and dicyclopentadiene resin. Further, in the specification and the patent application, the "photosensitive resin" and the "thermosetting resin" each contain not only a resin after curing but also a polymerizable monomer and/or oligomer. Further, as the other polymerizable compound, a binder resin having an acidic group or a resin used in a general ink such as an acrylic resin or a urethane resin may be used as the other polymerizable resin. [Solvent] The pigment dispersion may be aqueous or non-aqueous, and varies depending on the method of producing the color filter. For example, in the lithography method, it is preferably a non-aqueous system, and in the inkjet method, either of them may be used. . The solvent used in the colored composition of the present invention may, for example, be a fatty acid ester such as ethyl acetate, butyl acetate, ethylene glycol monomethyl ether acetate or propylene glycol monomethyl ether acetate, acetone or methyl group. Ketones such as ethyl ketone, methyl isobutyl ketone, cyclohexanone, and diacetone alcohol, aromatics such as benzene, toluene, and xylene, such as methanol, ethanol, n-propanol, isopropanol, and n-butanol Alcohols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, polyethylene glycol, propanol, monopropanol, dipropylene glycol, polypropylene glycol, trimethylene glycol, Glycols such as hexanetriol, glycerin, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, propofol monomethyl Alkylene glycol monoalkyl ethers such as hydroxy ether, propylene glycol monoethyl ether, triethylene glycol dimethyl ether, triethylene glycol diethyl ether, tetraethylene glycol dimethyl-36-201033292 ether, An alkanediol dialkyl ether such as tetraethylene glycol diethyl ether, an ether such as tetrahydrogen, dioxane or diethylene glycol diethyl ether, monoethanolamine, alkanolamine or triethylamine Alkanolamines such as alcohol amines, N,N-dimethylformamide, dimethylacetamide, N-methyl-2-pyrrolidone, 2-pyrrolidone, 1, methyl-2 a nitrogen-containing polar organic solvent such as imidazolinone or the like, water or the like. The water-soluble ones of these solvents can be mixed with water and used as an aqueous one. Further, it may be mixed with a solvent selected from the above solvents other than water as an oily medium. In the colored composition for a color filter of the present invention, one or more kinds of dispersing agents selected from the group consisting of a surfactant, a polyoxygen additive, a decane coupling agent, and a coupling agent are preferred. These dispersing agents are also used in combination of two or more kinds. Specific examples of the aforementioned dispersing agent will be described below. The surfactant is not particularly limited as long as it has an interfacial activity, and examples thereof include cationic, anionic, nonionic or amphoteric surfactants. Specific examples thereof include alkanesulfonates and linear benzenesulfonates. Acid salt, branched alkylbenzene sulfonate, alkylnaphthalene sulfonate, naphthalene sulfonate condensate, alkyl sulfate, polyoxyethylene alkyl ether sulfate phosphate, polyoxyethylene alkyl ether phosphate And anionic surfactants such as aliphatic monocarboxylic acids, sub-surfactants such as alkylamine salts and quaternary amine salts, glycerin fatty acid esters, sorbitan fatty acid polyoxyethylene alkyl ethers, polyoxidation a non-interfacial surfactant such as vinyl alkyl phenyl ether, poly diglycolate, and polyoxyethylene sorbitan fatty acid ester, or an amphoteric surfactant such as alkyl betaine, which may be furan diethyl hydrazine. , Ν-3-dimediate species with more titanium-containing groups of alkyl acid salts, alkanoate male esters, alcoholic cations -37-201033292 sub-, anionic, nonionic Polymer interface of any of the two sexes Of the agent. Specific examples of the polyoxymethylene-based additive include polyalkyl siloxanes, polyalkyl phenyl siloxanes, polyorganosiloxanes, polydimethyl siloxanes, and polyorganosiloxane polyethers. Copolymers, polyfluoro havees, organic decanes, and the like. These polyoxo-based additives may be used in combination of two or more kinds. Specific examples of the decane coupling agent include vinyl trimethoxy decane, vinyl triethoxy decane, vinyl tris(methoxy-methoxyethoxy) decane, /3 - (3, 4) -Epoxycyclohexyl)ethyltrimethoxydecane, r-glycidoxypropyltrimethoxydecane, glycidoxypropylmethyldiethoxydecane, τ-aminopropyltri Ethoxy decane, N-phenyl-r-aminopropyltrimethoxydecane, r-methacryloxypropyltrimethoxydecane, vinyltriethoxydecane, methyltrimethoxy Decane, dimethyldimethoxydecane, phenyltrimethoxydecane, diphenyldimethoxydecane, methyltriethoxydecane, dimethyldiethoxydecane, phenyltriethoxy Decane, diphenyldiethoxydecane, n-butyltrimethoxydecane, isobutyltrimethylmethoxydecane, trimethylmethoxydecane, hydroxypropyltrimethoxydecane, n-hexadecyltrimethyl Oxydecane, n-octadecyltrimethoxydecane, and the like. Specific examples of the titanium-based coupling agent include isopropyl tris(N-amineethylamine ethyl) titanate and dibutoxybistriethanolamine titanate. The amount of the dispersant to be used is also preferably from 0.1 to 100 parts by mass, particularly preferably from 0.5 to 80 parts by mass, per 100 parts by mass of the organic pigment, depending on the kind of the dispersant to be used. The method of using the dispersing agent is not particularly limited, and the method of modulating the coloring composition for the lithography method known from the Japanese Patent Publication No. -38-201033292 can be used. The present invention also provides a color filter obtained by using the above-described coloring composition for a color filter. The color filter shows high contrast and good light transmission. Specifically, in the wavelength of 650 nm, it is preferable to exhibit light transmittance of 85% or more, more preferably 90% or more. In order to produce the color filter of the present invention, any well-known method can be used, and a lithography method and an inkjet method are suitably used. The lithography method and the inkjet method will be described in detail below. ❾ (1) lithography method When a color filter is formed by the lithography method, a photosensitive resin is used as the polymerizable compound for the coloring composition for a color filter of the present invention. The photosensitive resin is blended in a coloring composition together with a photopolymerization initiator as a monomer and/or an oligomer, and is cured by light irradiation to form a film on a transparent substrate. As the photosensitive resin, a polymer or copolymer having a polymerizable monomer having one or more ethylenic double bonds in the molecule is suitable. ❹ As such a photosensitive resin (polymerizable monomer), acrylate and methacrylate are particularly preferable, and specific examples thereof include methyl acrylate, methyl methacrylate, butyl methacrylate, and butyl acrylate. Pentaerythritol tetraacrylate, pentaerythritol tetramethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol hexaacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol penta methacrylate Ester, glycerin diacrylate, glycerin dimethacrylate, 1,4-butanediol diacrylate, 1,4-butanediol dimethacrylate, bis-39-201033292 phenol A diacrylate, double Phenol A dimethacrylate and the like. When the lithography method is used, in the coloring composition for a color filter of the present invention, a binder resin having an acidic group is used in addition to the above-mentioned photosensitive resin. The binder resin having an acidic group may, for example, be a resin having a carboxyl group, a hydroxyl group or a sulfonic acid group, and is preferably a binder resin having a carboxyl group and/or a hydroxyl group. As the above-mentioned binder resin having an acidic group, it is preferably selected from the group consisting of acrylates, methacrylates, styrene, vinyl acetate, vinyl chloride, N-vinylpyrrolidone, and acrylamide. a monomer having an ethylenic double bond and an ethylenic double bond having an acidic group selected from acrylic acid, methacrylic acid, p-styrenecarboxylic acid, p-styrenesulfonic acid, p-hydroxystyrene, and maleic anhydride Copolymer of monomer. The binder resin having an acidic group is preferably used in an amount of 0.5 to 4 parts by mass, more preferably 1 to 3 parts by mass, per 1 part by mass of the photosensitive resin (polymerizable monomer), and is used as a lithography method. The solvent used in the coloring composition may be exemplified by ® fatty acid esters, ketones, aromatics, alcohols, glycols, glycerin, alkylene glycol monoalkyl ethers, and alkylene glycol dialkyl ethers. One or more oily media selected from ethers and nitrogen-containing polar organic solvents. The amount of the solvent to be used is preferably from 3 to 30 times by mass, particularly preferably from 4 to 15 times by mass, based on the total mass of the components other than the solvent in the coloring composition. Further, in the coloring composition for the lithography method of the present invention, in addition to the above-mentioned components, a wetting agent, an anti-fading agent, and an emulsion stabilizer may be mentioned as needed -40-

201033292, a well-known additive such as a UV absorber, a preservative, an antifungal agent, a pH adjuster, a surface conditioner, an antifoaming agent, a viscosity adjuster, a dispersion stabilizer, and a rust preventive agent (Japanese Patent Laid-Open Publication No. 2003-306623) The various additives may be added in an oil phase or an aqueous phase during preparation. The coloring composition for a color filter of the present invention may be one by one.

a mill, a three-roll mill, a homogenizer, a kneader, a vibrating disperser, etc., and the steps of uniformly mixing and dispersing the pigment composition, the polymerizable compound, and other various additives of the present invention, and before use The agent or the like is used to perform the viscosity adjustment step. The method of forming a color filter on a display substrate using the coloring composition for a color filter of the present invention can be carried out by using a well-known lithography method, for example, a color filter can be obtained by a method comprising a printing method , a spray method, a bar coating method, a roll coating method, a spin coating method, and the like, wherein the colored composition of the present invention is uniformly coated on a display substrate, and the step of heating to remove the solvent in the ink is used. The step of exposing the color filter pattern on the substrate, such as high pressure water, the alkali, the washing step, and the baking step. (2) When the inkjet method is used to form a color filter by the inkjet method, the polymerizable compound which is a coloring composition for a filter of the present invention is not particularly useful as long as it is used by an inkjet ink. For the limitation, a single system of any of the photo-resin and/or the thermosetting resin can be used. Examples of such a photosensitive resin include an acrylic resin, a methyl tension, and a chelate method. The two-roller agent and the solution plate are used. For example, the silver lamp is used in the color step by knowing the steps. Acrylic -41- 201033292 Acid resin and epoxy resin, etc., acrylic resin and methacrylic resin are preferred. Acrylic resin and methacrylic resin, preferably combined by acrylate, methacrylate, urethane acrylate, urethane methacrylate, acrylamide, methacrylamide, alkyl acrylate a selected photopolymerizable monomer such as ester, benzyl methacrylate, benzyl acrylate or aminoalkyl methacrylate, and a benzophenone derivative, an acetophenone derivative, a benzoin derivative, A photopolymerization initiator selected from a compound such as a benzoin ether derivative, a thioxanthone derivative, an anthracene derivative, a naphthoquinone derivative or a triterpene derivative. Further, in addition to the photopolymerizable monomer, a photopolymerizable monomer having a hydrophilic group such as acrylic acid, methacrylic acid, maleic acid or vinyl acetate may be added. Examples of the thermosetting resin include melamine resin, urea resin, alkyd resin, epoxy resin, phenol resin, and cyclopentadiene resin. When the inkjet method is used, the solvent used in the colored composition may be an oily medium or an aqueous medium, and an aqueous medium is more suitable. The aqueous medium is water or a mixed solvent of water and a water-soluble organic solvent, and is preferably a mixed solvent of water and a water-soluble organic solvent. Further, it is preferred to use a deionized processor. The oily medium to be used in the coloring composition is not particularly limited, and for example, a solvent used as a coloring composition for lithography can be used. Examples of the solvent used in the aqueous medium include alcohols, ketones, ethers, glycols, glycerin, alkylene glycol monoalkyl ethers, alkylene glycol dialkyl ethers, and alkanolamines. And a nitrogen-containing polar organic solvent or the like which is selected to have water solubility. These water-soluble organic solvents may be used singly or in combination of two types -42 - 201033292 or more. The amount of use of the solvent is not particularly limited, and the viscosity of the colored composition is 20 mPa*s or less at room temperature, preferably 10 mPa·s or less, and the amount of use can be appropriately adjusted. The coloring composition of the present invention can be prepared by a method including a step of dispersing and mixing the components, similarly to the coloring composition for lithography. The dispersing agent may be blended in the same manner as in the lithography method as needed during the dispersion. Further, in the coloring composition of the present invention, in addition to the above components, a wetting agent, an anti-fading agent, an emulsion stabilizer, an ultraviolet absorber, a preservative, an antifungal agent, a pH adjuster, and a surface tension adjustment may be contained as required. Various known additives such as a solvent, an antifoaming agent, a viscosity modifier, a dispersion stabilizer, and the like, and a method of forming a color filter using the coloring composition obtained as described above, as long as the color is formed by a known ink jet method The method of the filter is not particularly limited. For example, a color filter can be formed by a method comprising the steps of forming a specified color-color filter pattern in droplet form on a display substrate, drying it, and performing heat treatment or light irradiation. Or the step of hardening and film-forming the color filter pattern on the substrate. The lithography method and the ink jet method have been described above, but the color filter of the present invention can also be obtained by other methods. When a color filter forming method (for example, various printing methods such as a lithography method) other than the above is used, when the coloring composition contains the polymerizable compound and a solvent, an azo compound represented by the formula (1) is used as a coloring agent. Then, the color-43-201033292 coloring composition for the filter and the obtained color filter are also included in the scope of the present invention. For example, the components for forming a polymerizable compound, a solvent, an additive, and the color filter can be selected according to conventional examples, and are not limited to those described in the above description of the lithography method and the inkjet method. As the color filter of the present invention obtained as above, a color filter pattern of G (green) and B (blue) and a pixel can be formed by a well-known method. This filter is capable of giving a liquid crystal display having very high transparency, excellent spectral characteristics, small depolarization effect, and capable of displaying a clear image. As a method of forming a color filter, there is a method of forming a pattern by a photoresist first, followed by a method of dyeing, or a method disclosed in Japanese Laid-Open Patent Publication No. Hei No. Hei. No. Hei. A method of forming a pattern by adding a photoresist to a pigment. As a method for introducing the dye of the present invention into a color filter, any of these methods can be used. As a preferred method, the content described in JP-A-1-475753 or JP-A-6-35182 can be mentioned. a positive photoresist composition made of a thermosetting resin, a quinonediazide compound, a crosslinking agent, a dye, and a solvent, and coated on the substrate, exposed to a photomask, and exposed to the exposed portion On the other hand, a positive resist pattern is formed, and the positive resist pattern is subjected to overall exposure, and then the exposed positive resist pattern is cured to form a color filter. Further, by forming a black matrix in accordance with a usual method, an RGB primary color system or a Y, M, C complementary color system color filter can be obtained. In the case of the color filter, the amount of the organic pigment used in the pigment composition of the present invention is not limited, but is preferably 0.1 to 50% by mass. -44-.201033292 It is preferable to use the thermosetting resin, the quinonediazide compound, the crosslinking agent, and the solvent used in this case, and the amount thereof to be used. EXAMPLES Hereinafter, the present invention will be specifically described on the basis of examples, but the present invention is not limited by the examples. Hereinafter, the parts mean parts by mass. The X-ray diffraction measurement of the crystalline form azo pigment is carried out by the powder X-ray diffraction measuring apparatus RINT25 00 (manufactured by Rigaku Co., Ltd.) in accordance with Japanese Industrial Standard JISK013 1 (General Rules for X-ray Diffraction Analysis), using a CuKa line, It is carried out under the following conditions. Tester used: Rigaku's automatic X-ray diffraction device RINT2500 X-ray tube ball: Cu tube voltage: 55KV Tube current: 280mA Scanning method: 20/0 scanning scanning speed: 6deg./min Sampling interval: O.lOOdeg. Angle (2Θ) : 5deg. Stop angle (2Θ) : 55deg. Diffusion seam: 2deg. Scattering seam: 2deg. Receiving seam: 0.6 mm Using vertical goniometer -45- 201033292 α-type azo pigment (D-1) The /3 type azo pigment (D-2) is synthesized by a route.

[Synthesis Example 1] Synthesis of α-type azo pigment (D-1) 20 g of the compound represented by the formula (2) was added to 200 ml of phosphoric acid, completely dissolved at room temperature, and the solution was ice-cooled and kept at At -5 °C, 8.0 g of sodium nitrite was added and stirred for 40 minutes, then 3·3 g of sodium nitrite was added, and the mixture was further stirred for 20 minutes. To the reaction liquid, 1.5 g of urea was added to obtain a diazo gun salt solution. In a solution of 21 g of the compound of the formula (3) dissolved in hydrazine, dimethyl-dimethyl acetamide (DMAc) (400 ml), while maintaining the diazonium salt solution at 5 to 10 ° C It costs 80 minutes to drip. The obtained solution was stirred at 5 to 10 ° C for 2 hours, and then 240 ml of methanol was added thereto, and the mixture was further stirred for 10 minutes. The precipitated crystals were separated by filtration and washed with 3 mL of methanol. The crystals were dried without adding 500 ml of water and 50 ml of saturated sodium hydrogencarbonate for neutralization. The mixture was dried at 5 (TC for 24 hours) using a blow dryer. After the obtained crystal was suspended in 400 mL of DMAc, the mixture was stirred at 80 ° C for 30 minutes, and then 300 ml of pure water was added thereto, and the mixture was stirred at 80 ° C for 30 minutes. Then, -46-201033292, it was cooled to room temperature for two hours, and the obtained crystal was separated by filtration at room temperature for 24 hours, and dried in a vacuum dryer at 50 ° C for 10 hours to obtain 25.6 g of α-form crystal form. Azo pigment (D-1), yield: 73%. The X-ray diffraction of the obtained α-form crystal form azo pigment was measured under the above conditions, and the result was 7.1 at the Bragg angle (20 ± 0.5 · 5°). , 25.3, 26.0, and 27.2. X-ray diffraction peaks showing characteristics. The Cu-characteristic X-ray diffraction pattern is shown in Fig. 1. [Synthesis Example 2] Synthesis of anthraquinone azo pigment (D-2) 20 g of the compound of the formula (2) was added to 2 ml of phosphoric acid 'to dissolve completely at room temperature, and the solution was ice-cooled, kept at -5 ° C. 'Add 8.0 g of sodium nitrite, stir 40 Minutes, then add 3.3 grams of sodium nitrite and stir for a further 20 minutes. Add 1.5 mL of urea to the reaction solution to obtain diazo iron. a salt solution, which is dissolved in a solution of 21 g of the compound of the formula (3) in hydrazine, hydrazine-dimethylacetamide (DMAc) (400 ml), while maintaining the diazonium salt solution at 5 to 1 The solution was added dropwise for 80 minutes, and the resulting solution was stirred at 5 ® to 10 ° C for 2 hours, then 240 ml of methanol was added, and the mixture was further stirred for 10 minutes. The precipitated crystals were separated by filtration and washed with 300 ml of methanol. The crystal was dried, and the crystal was dried, and 500 ml of water and 50 ml of saturated sodium hydrogencarbonate were added to neutralize. The obtained crystal was suspended in 40 mL of DM Ac, and stirred at 8 ° C for 30 minutes, and then 300 ml was added. The pure water was stirred at 80 ° C for 30 minutes. Then, it was cooled to room temperature for two hours, and the obtained crystal was separated by filtration, and dried at room temperature for 24 hours at room temperature in a vacuum dryer at 50 ° C for 1 hour. In an hour, 26.0 g of a crystalline form of azo pigment (D-2) -47-201033292 was obtained. Yield 7 4 %. Obtained under the above conditions; X-ray diffraction measurement of type 5 crystal form azo pigment The result is 7.1, 117, 20.0° and 27.1° at the Bragg angle (20 ± 〇. 5 °). Fig. 2 shows a CuKa characteristic X-ray diffraction pattern. [Example 1] Preparation of Pigment Dispersion 1 2.5 parts of α-form crystal form azo pigment synthesized in Synthesis Example 1 and 0.5 part of sodium oleate were mixed. 5 parts of glycerin and 42 parts of water were dispersed for 6 hours at 300 revolutions per minute using a planetary crucible ball mill together with 100 parts of 0.1 mm diameter chrome oxide beads. After the end of the dispersion, the oxidized cone beads were separated to obtain a red pigment dispersion 1 (volume average particle diameter; Mv and 82 nm: measured by Nanotrac 150 (UPA-EX150) manufactured by Seiko Co., Ltd.). [Example 2] Preparation of Pigment Dispersion 2 2.5 parts of the azo pigment of the type 3 crystal form synthesized in Synthesis Example 2, 0.5 part of sodium oleate, 5 parts of glycerin, and 42 parts of water were mixed, and a planetary type was used. The ball mill was dispersed with 100 parts of 0.1 mm diameter zirconia beads for 6 hours at ® 300 revolutions per minute. After the completion of the dispersion, the zirconia beads were separated to obtain a red pigment dispersion 2 (volume average particle diameter; Mv and 82 nm: measured by Nanotrac 150 (UPA-EX 150) manufactured by Nikkiso Co., Ltd.). [Comparative Example 1] Preparation of Comparative Pigment Dispersion 1 In the same manner as in Example 1, except that CI Pigment Red 254 (B-CF manufactured by Ciba Specialty Co., Ltd.) was used instead of the α-type crystal form azo pigment used in Example 1. A red comparative pigment dispersion 1 was obtained. (Evaluation) -48-201033292 <Coloring power evaluation> Each of the pigment dispersions obtained above was applied to Seiko Epson's Photomat <Pigment-specific> paper using a bar coater of Νο.3. The image density of the obtained coating material was measured by a reflection concentration meter (X-Rite 93 8 manufactured by X-Rite Co., Ltd.), and "coloring power (OD: optical density)" was evaluated by the following criteria. The results are shown in Table 1. ◎ ; OD 値Μ 1.6 or more 〇: OD 値 is 1.4 or more and less than 1.6 △ : OD 値 is 1.2 or more and less than 1.4 X : OD 値 is less than 1.2 < Evaluation of solvent resistance > Solvent resistance Each of the α-type crystal form azo pigment represented by the formula (1) used in the pigment dispersion 1 (solid example 1) and the CI pigment red 254 used in the comparative pigment dispersion 1 (compared to the carrier example 1) The l〇mg pigment was suspended in 50 mL of N-methylpyrrolidone, and when it was heated at an internal temperature of 60 ° C for 1 minute, the fully dissolved one was evaluated as X, and the incompletely dissolved one was evaluated as 〇. <Hue evaluation> The method used for the evaluation of the coloring power described above was judged by the following three visual criteria in the reflection spectrum of the coating material having an OD of 1.0. Judgment (1) No yellow tone (2) No blue tone (3) Bright. -49- 201033292

X conditions, the situation of the situation of the foot 2 1 to meet the fullness of the fullness of the situation &lt; light resistance evaluation> The coloring power evaluation used to apply the image concentration of 1.0 coating, use The fading meter 'irradiated on the 14th day (170000 lux; in the presence of a cut filter of 325 nm or less), and the image density before and after the 氙 irradiation was measured using a reflection densitometer 当作' as the residual rate of the pigment [(concentration after irradiation / before irradiation) Concentration) xl〇〇%] was evaluated. The results are shown in Table 1. [Table 1] Pigment coloring power solvent-resistant hue light resistance Example 1 Pigment dispersion 1 U-type crystal product form azo pigment (D-1)) ◎ 〇 ◎ 88.8 Example 2 Pigment dispersion 2 (/? Form azo pigment (D-2)) 〇〇〇95 Comparative Example 1 Comparative Pigment Dispersion 1 (CI Pigment Red 254) Δ 〇〇62.3 As is apparent from the results of Table 1, the α-form crystal form pigment of the present invention is It exhibits high solvent resistance and is particularly excellent in coloring power and hue when used as a pigment dispersion. On the other hand, the β-form crystal form pigment of the present invention exhibits particularly high solvent resistance, and at the same time, when used as a pigment dispersion, -50-201033292 is excellent in coloring power and solvent resistance. Therefore, the pigment dispersion of the pigment of the present invention can be applied, for example, to an ink for printing such as inkjet. [Example 3] A polymer dispersant represented by Dispersant 10 described on page 22 of the International Publication No. W006/064193 manual was neutralized with an aqueous potassium hydroxide solution. 30 parts by mass of the above-mentioned synthesized azo pigment (D-1) and 95 parts by mass of ion-exchanged water were added to 75 parts by mass of the obtained aqueous dispersion liquid solution (solid content concentration: 20%), and the stirring wings were dispersed by stirring. To carry out mixing and coarse dispersion. To the mixed and coarsely dispersed liquid, 600 parts by mass of zirconia beads were placed, and this was dispersed in a classifier (sand mill) for 4 hours, and then the beads and the dispersion were separated. While stirring the resulting mixture, 2 parts by mass of polyethylene glycol diglycidyl ether was slowly added at 25 t, and stirred at 50 ° C for 6 hours. Furthermore, an ultrafiltration membrane having a sub-number of 300 K was used to remove impurities, and a filter having a pore size of 5; arn (acetonitrile membrane, outer diameter: 25 mm, manufactured by Fujifilm Co., Ltd.) was attached. The syringe having a capacity of 20 ml was filtered to remove the coarse particles to obtain a pigment dispersion 3 having a solid concentration of 10% (particle diameter: 80 nm: measured by Nanotrac 150 (UPA-EX150) manufactured by Seiko Co., Ltd.) [ Comparative Example 2] A comparative pigment dispersion 2 was obtained in the same manner as in Example 3 except that instead of the compound D-1 used in Example 3, Comparative Example 1 was used. [Example 4] The pigment dispersion obtained in Example 3, which is 5% by mass in terms of solid content, 3% by mass of glycerin, 5% by mass of 2-pyrrolidone, and 2% by mass - 51 - 201033292% 1,2-hexanediol, 2% by mass of triethylene glycol monobutyl ether, and 〇·5 mass. / 〇 〇 丙 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 、 A 20 ml syringe was used to filter the resulting mixture, and the coarse particles were removed to obtain the pigment ink 3 of the present invention. [Comparative Example 3] In place of the pigment dispersion 3 obtained in Example 3, the comparative pigment obtained in Comparative Example 2 was used. Comparative Pigment Ink 4 was obtained in the same manner as in Example 4 except for the dispersion 2. In addition, in Table 2, "spit out stability", "light fastness", "heat fastness", "ozone fastness", "metal luster", "ink liquid stability" It is mounted in the yellow ink cartridge of Seiko Epson Co., Ltd. inkjet printer PX-V630. The other inks are PX-V630 pigment ink, and the photo system is Seiko Epson. Co., Ltd. photo paper &lt; Gloss &gt; and Seiko Epson Co., Ltd. photo paper CrisPia &lt;High Gloss &gt; 'The monochrome image pattern of the beautiful step-like density change recommended on it and green, red, Gray image pattern for image quality and ink ejection and image fastness evaluation. Evaluations other than metallic luster were performed in a single color. The following evaluations were carried out for the inkjet inks of the above-described Example 4 (pigment ink 4) and Comparative Example 3 (comparative pigment ink 3). The results are shown in Table 2. (Evaluation test) -52- 201033292 (1) Fixing the ink sputum on the printer. </ STRONG> After confirming that the ink was discharged from all the nozzles, 20 sheets of A4 were output and evaluated by the following criteria. A: There is no erroneous printing from the start to the end of the printing. B: An output C is generated. The printing is confusing from the start to the end of the printing. (2) For the image preservability, the following samples are used. Evaluation. ® [1] Light Fastness X-Rite photographic density meter 310 (x-rite 3 10) was used to measure the image density Ci immediately after printing, and the image was illuminated with an ATLUS climatometer. (100,000 lux) After 1 day, the image density Cf was measured again, and the image residual ratio Cf/Cixl00 was obtained and evaluated. The reflection density related to the image afterimage rate is evaluated at three points of 1, 1.5, and 2, and the image residual rate is 80% or more at any concentration, and 1 or 2 points are not reached. 80% of the cases are treated as B, and all cases where the concentration is less than 80% are treated as C. ^ [2] Regarding the thermal fastness, the concentration of the printed sample was stored for 7 days at 80 ° C and 60% RH, and the concentration was measured by the reflection concentration meter X_Hte 3 10 to obtain the image residual ratio. Conduct an evaluation. The reflection density of the image afterimage rate is evaluated by three points of 1, 1.5, and 2, and the image residual rate is 95% or more at any concentration, and 1 or 2 points are less than 9 The case of 5% is regarded as B, and the case where all the concentrations are less than 95% is regarded as C. [3] About ozone resistance (ozone fastness), placed in a box with an ozone gas concentration set at 5 ppm (25 ° C, 50%) for 14 days, using a reflection concentration of -53-201033292 X-Rlte 310 The image density before and after the ozone gas was placed was measured and evaluated as the image residual ratio. Further, the reflection concentration was measured at three points of 1, 1.5 and 2. The ozone gas concentration in the tank was set using an APPLICS ozone gas monitor (model: OZG-EM-01). The case where the image residual rate is 80% or more at any concentration is regarded as A, the case where 1 or 2 points is less than 80% is regarded as B, and the case where all the concentrations are less than 70% is regarded as C, Evaluate in three levels. (3) The presence or absence of metallic luster: The yellow, green, and red prints are visually observed by reflected light. Those who did not see the metallic luster were evaluated as "〇", and those who saw the metallic luster were evaluated as ^X". (4) Ink stability: When the pigment inks of the examples and the comparative examples were passed at 60 ° C for 10 days, the particle size in the pigment ink was not changed as "〇", and the particle size was determined. The changer is evaluated as "X". It is shown in Table 2 below. [Table 2] Ink is subjected to image discharge, stable light fastness, fast fastness, ozone fastness, metallic luster, ink stability pigment, Example 4 Gloss AAAA 〇〇D-1 Example 4 High gloss AAAA 〇〇D-1 Comparative Example 3 Gloss BCA c 〇X Comparative Compound 1 Comparative Example 3 High gloss B c A c 〇X Comparative Compound 1

As a result of the results of Table 2, the pigment ink using the pigment of the present invention is excellent in spoutability and fastness, and suppresses the occurrence of metallic luster, and the pigment ink-54-201033292 is excellent in stability. From the results of Table 2, it is understood that the system using the ink of the present invention is excellent in performance. In particular, it is excellent in light fastness, ozone fastness, and ink stability with respect to the comparative examples. [Example 5] Using the pigment ink prepared in Example 4, the image was printed on the inkjet paper glossy paper made by Fujifilm Co., Ltd. by PX-V630 manufactured by Epson Co., Ltd. In the same manner as in Example 7, the same results were obtained. As is clear from the results of Tables 1 and 2, the pigment dispersions 1 to 3 and the pigment ink 4 of the pigment of the present invention are excellent in color tone, and exhibit high coloring power and light resistance. Therefore, the pigment dispersion of the pigment of the present invention can be applied, for example, to an ink for printing such as inkjet. [Example 201] [Color filter produced by lithography] ® The α-type crystalline form azo pigment (D1) synthesized in Synthesis Example 1 was used. The material shown below was placed in a 70 ml of a cannabis bottle and shaken for 6 hours in a vibrating disperser (DAS 200 manufactured by LAU Co., Ltd.) to obtain a pigment dispersion 201. -55- 201033292 [Table 3] (composition of pigment dispersion 201) α-type crystal form azo pigment (ΕΜ) 0.6 g of 1,2-propanediol-1-monomethyl ether 2-acetate (Tokyo Chemical Co., Ltd.) 5.0 g of chrome oxide beads (φ0·3ππη) 10 g [Example 202] In place of the α-type crystalline form azo pigment (D-1) used in Example 201, a cold-type crystalline form azo pigment (D-) was used. 2) The pigment dispersion 202 was obtained in the same manner as in Example 201. [Evaluation of the stability of the pigment dispersion over time] The pigment dispersions 201 to 202 and the comparative pigment dispersions 201 and 202 prepared in Examples 201 and 202 and Comparative Examples 201 and 202 were stored in the dark at room temperature for 2 weeks. The degree of precipitation of the foreign matter was visually evaluated in accordance with the following criteria. &lt;Judgement criteria&gt; 〇: No precipitation was observed. △: The precipitation was slightly observed. χ · See the precipitation. [Table 4]

Pigment Dispersion Pigment Dispersion Stability over Time Example 201 Yankee Dispersion 201 D-1 〇 Example 202 Yankee Dispersion 202 D-2 〇 Comparative Example 201 Comparison of Yankee Dispersion 201 PR254 △ Comparative Example 202 Comparison Pigment Dispersion 202 Compound X-56-201033292 of the formula [I] The pigment dispersions 201 and 202 of the present invention containing the azo compound represented by the formula (i) as a colorant, and the pigments of Comparative Examples 201 and 202 were used. In comparison, the foreign matter caused by the passage was observed, and the dispersion was excellent in stability over time. [Example 2 0 3] The coloring composition 201 for a color filter for lithography was prepared by adding the material shown below to the pigment dispersion 201 by further shaking for 30 minutes by the above-described vibrating disperser. [Table 5] (Composition of Color Composition 201 for Color Filter) Pigment Dispersion 201 15.6 g of photosensitive tree should be 2.5 g (made by Daicel Chemical Co., Ltd., Cyclomer P200) 0.2 g of pentaerythritol tetraacrylate (manufactured by Aldrich Co., Ltd.) 2-benzyl-2-dimethylamino-4'-morpholinylphenylpropyl ketone 0.05 g (manufactured by Aldrich) 2,4-diethyl-9H-thioxan-9-one 0.05 g ( Tokyo Chemical Co., Ltd.) 1,2-propanediol 1-monomethyl ether 2-acetate 0.8 g (manufactured by Tokyo Chemical Industry Co., Ltd.) cyclohexanone 0.2 g (manufactured by Tokyo Chemical Industry Co., Ltd.) [Example 204] Color filter was obtained in the same manner as in Example 203 except that instead of the crystallization type azo pigment-57-201033292 (D-1) used in Example 203, a cold crystal form azo pigment (D-2) was used. Coloring Composition 202 for Light Films [Examples 205, 206] The color filters obtained in the above Examples 203 and 204 were coated with the coloring compositions 201 and 202 using a bar coater Rod No. 10. After the glass was dried, it was dried in an oven at 80 ° C for 5 minutes to obtain an ink coating film. After a part of the coating film was appropriately shielded, it was irradiated under a condition of 200 m J/cm 2 using a high pressure mercury lamp to expose the coating film. Then, development was carried out at 25 ° C using a 0.5% aqueous sodium carbonate solution, and further dried in an oven at 220 ° C for 20 minutes to prepare color filters 205 and 206. The light transmittance of this color filter was measured using a spectrophotometer (manufactured by Hitachi, Ltd., U-3310). Further, the transmittance of the obtained color filter was found to be 5% of the wavelength between 540 and 610 nm. The results are shown in Table 5. [Example 207] In Example 201, for 0.6 g of the α-form crystal form azo pigment (D-1), 0.5 g of a surfactant as a dispersing agent (pigment of the company) was further added. The wet dispersant ΒΥΚ-161) was dispersed, and as a result, a color filter 207 having the same performance as that of Example 211 was obtained at a dispersion time of 6 hours. [Comparative Examples 201 and 202] In place of the α-type crystalline form azo pigment (D-1) used in Example 201, CI Pigment Red 254 (IRGAPH〇RE DPP RED, manufactured by Ciba Specialty Chemicals Co., Ltd.) was used. A color filter was prepared in the same manner as in Example 201 except for the pigment represented by the following formula [Π]. The color obtained was measured -58-201033292 The transmittance of the filter was measured, and the wavelength with the lowest transmittance and the transmittance at 650 nm and the transmittance of 540 nm were obtained. The results are shown in Table 6.

© [Table 6] Transmittance of the lowest wavelength of the pigment transmittance of 650 nm, transmittance of 540 nm Example 205 D-1 571 nm 93% 2% Example 206 D-2 551 nm 90% 7% Comparative Example 201 CIPR254 564 nm 80% 8 % Comparative Example 202 Compound of the formula [I] 562 nm 65% 5% Using an α-type crystalline form azo pigment (D-1) containing a coloring agent and a β-type crystal form azo pigment (D-2) The color filters 205 and 206 made of the coloring composition of the color filter of the present invention have a transmittance curve which stands sharply, and has a high transmittance in the range of 650 to 750 nm, showing excellent transmission. Rate curve. Further, the color filter of Comparative Example 201 has a portion having a high transmittance at 540 nm. Further, the color filter of the coloring composition for a color filter of the present invention was compared with the color filter obtained in Comparative Example 201 and Comparative Example 202, and the transmittance of blue light of 350 to 400 nm was obtained. The system is very low, • 59- 201033292 can display red with high color purity. That is, the coloring composition for a color filter of the present invention can suitably adjust the wavelength of the sharp change in transmittance between about 540 nm and about 6 lOrun by selecting the structure of the azo compound represented by the formula (1). It is useful to obtain the red color of the most suitable hue at the wavelength of the light source corresponding to the backlight of the display. [Evaluation of heat resistance] Heat resistance tests were carried out using the color filters obtained in Example 205, Example 206, and Comparative Examples 201 and 202. &lt;Heat resistance test method&gt; The color filter was exposed to 250 ° C for 90 minutes, and the color difference (AESb) before and after the measurement was measured with a spectrophotometer (Macbeth Coloreye-3000, manufactured by SAKATA INX Co., Ltd.). The results were evaluated according to the following criteria, and the results are shown in Table 7. &lt;Criteria for determination&gt; 〇: Δ E*ab &lt; 1.0 Δ : 1 · 0 S △ E*ab &lt; 1 .1 X : 1 . 1 ^ Δ E*ab [Table 7] Pigment heat resistance test result color difference ( ΔE'b) Example 205 D-1 〇 Example 206 D-2 〇Comparative Example 201 PR254 X Comparative Example 202 Compound of the formula [I] Δ -60- 201033292 Using an α-form crystal form containing a coloring agent Color filters 205 and 206 made of the coloring composition for color filters of the present invention of azo pigment (D-1) and /3 type crystal form azo pigment (D-2), and Comparative Example 201 In the case of the pigment of Comparative Example 202, the heat resistance of the same or higher was exhibited. ' [Light resistance evaluation] A color filter prepared by using a fading meter was irradiated for 20 days of glare (1 700001 ux; in the presence of a 325 nm or lower cut filter, Suga test machine), and a spectrophotometer (SAKATA INX) The company's Macbeth Coloreye-8000) measured the color difference (△ E*ab) before and after it. The results were evaluated according to the following criteria, and the results are shown in Table 8. &lt;Criteria for Judgment&gt; ◎ : △ E*ab S 2.0 〇 : 2.0 &lt; Δ E*ab ^ 3.0

G Δ : 3.0 &lt; Δ E*ab$ 6.0 X : 6.0 &lt; AE*ab [Table 8] Pigment p photometric test result color difference (AE^b) Example 205 D-1 〇 Example 206 D-2 ◎ Comparative Example 201 PR254 X Comparative Example 202 Compound Δ of the formula [I] Examples 205 and 2 were prepared using a coloring composition containing a azo compound represented by the formula (1) as a coloring agent.彩色6 201033292 The color filter of the present invention shows the light resistance of the same or higher than that of the pigments of Comparative Examples 201 and 202. &lt;Comparative evaluation&gt; Using a comparative tester CT-manufactured by Nippon Electric Co., Ltd. 1 to determine the contrast of the color filters 205 and 206. The evaluation system comparison &amp; 230 00 is 〇, 23000> contrast 2 18000 is Δ, : 18000> contrast is X, and the results in Table 9 are not significant. [Table 9]

Pigment Comparative Example 205 D-1 〇 Example 206 D-2 〇Comparative Example 201 PR254 〇Comparative Example 202 Compound X of the formula [I] Using an α-type crystal form azo pigment containing a coloring agent (^: ^ And color filter 205 and 206 of Examples 205 and 206 of the color filter composition of the present invention, which is a crystalline form of azo pigment (D-2), and the pigment of Comparative Example 202. (Comparative Example 219) &lt;Preparation of Green Pigment Dispersion&gt; Preparation of a Green Pigment Dispersion Ρ1 - Mixing and Dispersing by 12.6 Parts as a Pigment by a Bead Mill cI pigment green 36 and CI pigment yellow 139 1 / 55 (mass ratio) mixture, 52 2 parts as a dispersant BYK2001 (Disperbyk: Beck Chemical (byk) public -62- 201033292 system, solid concentration 45.1% by mass), 2.7 parts of benzyl methacrylate/methacrylic acid copolymer as a dispersing resin (acid value 13 4 mgKOH/g, Mw = 3,000), 78_3 parts of propylene glycol monomethyl ether acetate as a solvent The resulting mixture was mixed for 15 hours to prepare a green pigment dispersion P 1. &lt;Red pigment dispersion Modulation&gt; Modulation of Red Pigment Dispersion P2 - Mixing and dispersing 12.1 parts of D-1 as a pigment and 1 000/45 (mass ratio) mixture of CI Pigment Yellow 139, 10.4 parts by a bead mill As a dispersing agent, BYK200 1 (Disperbyk: BYK), solid content concentration: 45.1% by mass, 3.8 parts of benzyl methacrylate/methacrylic acid copolymer as a dispersion resin (acid price: 134 mgKOH/ g, Mw = 30,000), 7 3.7 parts of a mixture of propylene glycol monomethyl ether acetate as a solvent for 15 hours to prepare a red pigment dispersion P2. &lt;Preparation of Blue Pigment Dispersion&gt; Preparation of Pigment Dispersion P3 - Mixing and dispersing 14 parts of CI Pigment Blue 15:6 as a pigment and 1 00/25 (mass ratio) mixture of CI Pigment Violet 23, 4.7 parts as dispersion by a bead mill BYK200 1 (Disperbyk: BYK), solid content concentration 45.1% by mass, 3.5 parts of benzyl methacrylate/methacrylic acid copolymer as a dispersion resin (acid price 134 mgKOH/g, Mw) =30,000) ' 7 7.8 parts of a mixture of propylene glycol monomethyl ether acetate as a solvent 15 small In the preparation of the blue pigment dispersion liquid P3. &lt;Preparation of the green coloring photosensitive composition (coating liquid) Ad> The above-mentioned green pigment dispersion liquid P1 is mixed in a manner of the following composition, and is mixed in the manner of -63-201033292 The coloring photosensitive composition A-1 was prepared by stirring. [Table 10] &lt;Composition&gt; The aforementioned green pigment dispersion P1 83.3 parts alkali-soluble resin: P-1 2.05 parts OXE-01 &lt;Ciba Specialty Chemicals Co., Ltd.; photopolymerization initiator) 1.2 parts of monomer 1 : KARAYAD DPHA (manufactured by Sakamoto Chemical Co., Ltd.) 1.4 parts of monomer 2; M-305 (manufactured by Toagosei Co., Ltd.) 1.4 parts of p-methoxyphenol 0.001 parts of polyethylene glycol methyl ether acetate [PGMEA (same as below) (solvent) 7 parts by weight of surfactant (trade name: F-781, manufactured by Dainippon Ink Chemicals Co., Ltd.), PGMEA 0.2% solution, 4.2 parts &lt; red coloring photosensitive composition (coating liquid) B-1 (Preparation) The coloring photosensitive composition B-1 was prepared by mixing and stirring so as to have the following composition, using the red pigment dispersion liquid P2. -64- 201033292 [Table 11] &lt;Composition&gt; The above red pigment dispersion P2 59.6 parts alkali-soluble resin: P-1 1.2 parts OXE-02 &lt;Ciba Specialty Chemicals Co., Ltd.; photopolymerization initiator) 0.7 parts Monomer 1 : KARAYADDPHA (manufactured by Nippon Kayaku Co., Ltd.) 1.6 parts of monomer 2 : SR-494 (manufactured by SARTOMER Co., Ltd.) 1.6 parts of p-methoxyphenol 0.002 parts of polyethylene glycol methyl ether acetate [PGMEA (hereinafter the same (slightly); solvent] 31 parts of surfactant (trade name: F-781, manufactured by Dainippon Ink Chemicals Co., Ltd.) 4.2 parts of PGMEA 0.2% solution &lt;blue coloring photosensitive composition (coating liquid) cl (Preparation) The coloring photosensitive composition C-1 was prepared by mixing and stirring in the following manner using the blue pigment dispersion liquid P3. -65- 201033292 [Table 12] &lt;Composition&gt; The above blue pigment dispersion P3 50.6 parts alkali-soluble resin: P-1 2_1 parts OXE-01 &lt;Ciba Specialty Chemicals Co., Ltd.; photopolymerization initiator) 1.2 parts Monomer 1 : KARAYAD DPHA (manufactured by Sakamoto Chemical Co., Ltd.) 1.2 parts of monomer 2 : SR-494 (made by SARTOMER) 3.5 parts of p-methoxyphenol 0.002 parts of polyethylene glycol methyl ether acetate [PGMEA (below) Similarly, a solvent; 36 parts of a surfactant (trade name: F-781, manufactured by Dainippon Ink Chemical Industry Co., Ltd.) PGMEA 0.2% solution 4.2 parts. _ The green coloring photosensitive composition prepared in the foregoing The material A-1 was applied onto a tantalum wafer formed by a device of 8 Å pre-sprayed with hexamethyldioxane to form a photocurable coating film. Then, the dried film thickness of the coating film was 1.0 Am, and heat treatment (prebaking) was performed for 180 seconds using a hot plate of loot. Then, using the i-line stepper exposure device FPA_ 3 000i5 + (manufactured by Canon), it is irradiated at 50 to 1 000 mJ/cm 2 through a Bayer pattern mask of l. 〇Aim at a wavelength of 3 65 nm (per 50 mJ/ Cm2 changes exposure). Then, the wafer on which the irradiated coating film was formed was placed on a horizontal rotary table of a rotary/spray developing machine (DW-30 type: CHEMITRONICS) -66-201033292, using CD-2000 A 40% dilution of Fujifilm Electronic Materials Co., Ltd. was subjected to puddle development at 230 ° C for 180 seconds, and a colored pattern was formed on the tantalum wafer. The germanium wafer on which the colored pattern is formed is fixed on the horizontal turntable by vacuum clamping, and the wafer is rotated by the number of revolutions of 50 rpm by the turning device, and is ejected from the nozzle from above the center of rotation Pure water is supplied as a spray and rinsed, followed by spray drying. Next, it was heated on a hot plate at 200 ° C for 5 minutes to obtain a color filter in which a ® pattern was formed. Further, in addition to the above-described red coloring photosensitive composition B-1 and blue photosensitive composition C-1, the exposure pattern was exposed through a 1.0/zm square island pattern mask, and the same steps as in green were repeated. And a color filter formed in a pattern of RGB is formed. When the camera module is manufactured using the apparatus in which the color filter is formed, it is confirmed that it has good spectral characteristics. Resin P-1 0 Acid value 54 mgKOH/g Mw : 15,000 Industrial use possibility The azo pigment or tautomer thereof of the present invention is excellent in coloring power and color matching, and is excellent in fastness (especially solvent resistance) ) is also excellent. Further, the pigment dispersion, the coloring composition, and the ink for inkjet recording of the present invention are obtained by dispersing the azo pigment of the present invention in various media, and having color characteristics, durability, and dispersion stability. Excellent. The present invention has been described in detail with reference to the specific embodiments thereof, and various modifications and changes can be made without departing from the spirit and scope of the invention. This application is based on the Japanese invention patent application filed on December 12, 2008 (Japanese Patent Application No. 200 8-31762 9) and the Japanese invention patent application filed on December 9, 2009 (Japanese Patent Application No. 2009-279405). The content is incorporated herein by reference. [Simplified Schematic Description] Fig. 1 shows the CuK α characteristic X-ray winding of the α-type crystal azo pigment shown by the formula (1) synthesized in Synthesis Example 1. Shooting. Fig. 2 is a diagram showing the CuK α characteristic X-ray diffraction pattern of the a-type crystal form azo pigment represented by the formula (1) synthesized in Synthesis Example 2. [Main component symbol description] None. ❹ -68-

Claims (1)

201033292 VII. Patent application scope 1. An azo pigment, its tautomer, salt, hydrate or solvate represented by the following formula (1) is a Bragg angle of x-ray diffraction in CuKa characteristics. (20±〇.5.) is represented by the following formula (1) of the characteristic X-ray diffraction peaks of 7.1°, 25.3°, 26_〇°, and 27.2°, (1) ❹ 2. An azo pigment, its tautomer, salt, hydrate or solvate, which is 7.1 in the Bragg angle (20 ± 0.5) of the CuK 〇: characteristic X-ray diffraction. , 11.7. 20.0. And 27.1. The characteristic X-ray diffraction peak is represented by the following formula (1), 3. A process for producing an azo pigment or a tautomer thereof represented by the following formula (1), which comprises a diazo gun salt derived from a heterocyclic amine represented by the following formula (2) The step of performing the azo coupling reaction of the compound represented by the formula (3), -69-201033292 ff (2) Ha 4. A process for the preparation of an azo pigment or a tautomer thereof according to claim 3 of the patent scope, which comprises supplying the formula (1) further to a drying step and a post-treatment step. 5. A process for the preparation of an azo pigment or a tautomer thereof according to claim 4 wherein the post-treatment step comprises heat treatment with a solvent having a solvent of SP to 7.0 to 14.0. 6. The method for producing an azo pigment or a tautomer thereof according to any one of claims 3 to 5, wherein the azo pigment represented by the formula (1) is in a CuKct characteristic X-ray diffraction of Prague The angle (2 &lt; 9 ± 0.5.) is 7.1. 25.3. , 26.0° and 27.2° characteristic X-ray diffraction peaks. 7. The method for preparing an azo pigment or a tautomer thereof according to the third item of Patent Application No. 3, which contains more in the coexistence of water, 1) Perform a post-processing step. 8. A process for the preparation of an azo pigment or a tautomer thereof according to claim 7 wherein the post-treatment step comprises heat treatment with a solvent having a solvent of SP to 7.0 to 14.0. 9. The method for producing an azo pigment or a tautomer thereof according to any one of claims 3, 7 and 8, wherein the azo pigment represented by the formula (1) is in a CuKa characteristic X-ray diffraction The Bragg angle (20 ± 〇.5.) is 7.1. , 11.7°, 20.0°, and 27.1° have characteristic X-ray diffraction peaks. -70- 201033292 10. A pigment dispersion characterized by containing an azo pigment, a tautomer, a salt, a hydrate or a solvate thereof in the first or second aspect of the patent application. A coloring composition characterized by containing a pigment dispersion of claim 10th. 12. An ink for inkjet recording, characterized by comprising a colored composition of claim 11 of the patent application. A colored composition for a color filter characterized by containing a colored composition of claim 11 of the patent application. A color filter comprising a color filter using the color filter of claim 13 of the patent application. A pigment dispersion characterized by containing an azo pigment, a tautomer, a salt, a hydrate or a solvate thereof in claim 6 of the patent application. 16. A coloring composition characterized by comprising a pigment dispersion of claim 15th. 17. An ink for ink jet recording, characterized by comprising a colored composition of claim 16 of the patent application. A colored composition for a color filter, which comprises the colored composition of claim 16 of the patent application. A color filter characterized by using a coloring composition for a color filter of claim 18 of the patent application. 20. A pigment dispersion characterized by containing -71-201033292 azo pigment, its tautomer, salt, hydrate or solvate of claim 9th. 21 _ - a coloring composition characterized by containing a pigment dispersion of the second aspect of the patent application. 2 2. An ink for inkjet recording characterized by containing a colored composition of claim 21 of the patent application. A colored composition for a color filter, which comprises the colored composition of claim 21 of the patent application. 0. A color filter ‘ is characterized in that it is produced by using a coloring composition for a color filter of claim 23 of the patent application. ❹ -72-