KR102116437B1 - Pigment composition, its manufacturing method, coloring composition, and color filter - Google Patents

Abstract

단, 일반식 (1)~(3)에서, X¹~X¹⁰은 수소 원자, 할로겐 원자, 알킬기, 퍼플루오로알킬기, 알콕실기, 카바모일기, 아세틸아미노기 등을 나타낸다.As a pigment composition containing an azo pigment represented by the following general formula (1) and an azo pigment selected from the following general formula (2) and the following general formula (3), the azo pigment represented by the general formula (1) and the general formula ( A pigment composition having a mass ratio of 60.0: 40.0 to 95.0: 5.0 with an azo pigment selected from 2) and general formula (3) is provided.

However, in the general formulas (1) to (3), X ¹ to X ¹⁰ represent a hydrogen atom, a halogen atom, an alkyl group, a perfluoroalkyl group, an alkoxyl group, a carbamoyl group, or an acetylamino group.

Description

Pigment composition, its manufacturing method, coloring composition, and color filter

The present invention relates to a pigment composition and its manufacturing method. In addition, the present invention relates to a coloring composition and a color filter using the same. Furthermore, the present invention relates to a color display device using a white light-emitting organic electroluminescent device (hereinafter also referred to as "organic EL device"), a red coloring composition for an organic EL display device used therein, and a color filter.

Organic pigments are known to have various chemical structures. In various coating or ink compositions, such as a color composition for a color filter, a color composition for an inkjet, a paint, etc., practically useful pigments exhibiting a vivid color tone, high brightness, high color strength, and excellent contrast usually have fine particles. However, when the pigment particles become fine, it becomes difficult to stabilize the dispersion composition such as offset ink, gravure ink, color composition for color filters, color composition for inkjet, and paints. Therefore, there is a fear of adversely affecting the manufacturing operation and the product obtained.

In recent years, in color filters used in liquid crystal display devices and the like, the demand for refinement of pigments has been very high for the purpose of improving brightness. However, it has been known that it is difficult to obtain dispersion stability of a dispersion composition using a fine pigment, and heat resistance and light resistance are deteriorated.

In the red filter segment of the color filter, diketopyrrolopyrrole pigment CI pigment red 254 and anthraquinone pigment CI pigment red 177 are often used alone or in combination.

CI Pigment Red 254 is a particularly excellent pigment, but has a problem in heat resistance of a fine pigment, and thus has a problem in that the brightness decreases in a color filter using the pigment. In addition, CI Pigment Red 177 has good heat resistance and light resistance, but has a problem of low brightness.

In Patent Documents 1 to 3, in order to further improve the brightness of the red filter segment, it has been proposed to use azo pigments such as CI Pigment Red 176, CI Pigment Red 242, and CI Pigment Orange 38 as a main pigment in a color filter. . However, the brightness is not sufficient, and further improvement is required.

Patent document 4 discloses an azo dye having a specific structure and a coloring composition containing the same. Although the azo dye described in Patent Document 4 is useful as a colorant, it is required to further improve physical properties such as brightness, heat resistance, and light resistance of a coating film (color filter) when used in a color filter.

1. Japanese Patent Publication No. 2009-237462 2. Japanese Patent Publication No. 11-14824 3. Japanese Patent Application Publication No. Hei 10-115709 4. Japanese Patent Publication No. 2011-173971

The problem to be solved by the present invention is to provide a pigment composition that is excellent in brightness of a coating film (color filter) and has no problems in other physical properties (heat resistance, light resistance, coating foreign matter), especially when used in a color composition for a color filter.

Further, an object of the present invention is to provide a color filter capable of satisfying two characteristics of high brightness and high purity in an organic EL display device using a white light-emitting organic EL element as a light source. Furthermore, an object of the present invention is to provide a color display device capable of achieving a high NTSC ratio, which is a quality required for color filters for organic EL display devices. Here, the NTSC ratio is the ratio of the area enclosed by the three primary colors, red (0.67, 0.33), green (0.21, 0.71), and blue (0.14, 0.08) in a standard manner determined by the National Television System Committee (NTSC). Means White refers to a broad concept, including pseudo white.

As a result of repeated examination of the inventors, the present inventors have found out that the above problem can be solved when a naphthol azo pigment having a specific structure forms a pigment composition in a specific ratio.

That is, Embodiment I of the present invention is a pigment composition containing an azo pigment represented by the following general formula (1) and an azo pigment selected from the following general formula (2) and the following general formula (3), It relates to a pigment composition characterized in that the mass ratio between the azo pigment represented by 1) and the azo pigment selected from the general formulas (2) and (3) is 60.0: 40.0 to 95.0: 5.0.

However, in the general formulas (1) to (3), X ¹ to X ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group, a perfluoroalkyl group, an alkoxyl group, a carbamoyl group, acetylamino group, 2-pyridylamino A carbonyl group or a group represented by the following formulas (a), (c) or (d) is shown.

However, in formula (a), n is an integer of 1-10 and R ¹¹ and R ¹² are alkyl groups. In formula (c), p and q are integers of 1 to 10 and R ¹³ to R ¹⁶ are alkyl groups. In formula (d), R ²¹ to R ²⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group, a perfluoroalkyl group, an alkoxyl group, an acetylamino group, a sulfo group and a metal salt thereof, or a group represented by formula (a).

It is preferable that X ¹ is a chlorine atom, X ⁴ is a trifluoromethyl group, X ⁶ is a hydrogen atom, a methyl group or a methoxy group, and X ² , X ³ , X ⁵ and X ¹⁰ are hydrogen atoms. It is preferable that X ⁹ is a group represented by formula (d).

In addition, Embodiment I is a coupler component having a mass ratio between a naphthol compound represented by the following general formula (4) and a naphthol compound represented by the following formula (5): 60.0: 40.0 to 100.0: 0, and a coupler component represented by the following general formula (6). The azo pigment represented by the general formula (1) is provided with a step of reacting a diazo compound of an aromatic amine having a mass ratio between the aromatic amine and the aromatic amine represented by the following general formula (7) 60.0: 40.0 to 100.0: 0. , It relates to a method for producing a pigment composition containing an azo pigment selected from formulas (2) and (3). However, the case where the mass ratio of the coupler component and the diazo compound of the aromatic amine are simultaneously 100.0: 0 is excluded.

However, in general formula (4), general formula (6) and general formula (7), X ¹ to X ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group, a perfluoroalkyl group, an alkoxyl group, a carbamoyl group, It represents an acetylamino group, a 2-pyridylaminocarbonyl group, or a group represented by the formulas (a), (c) or (d).

The mass ratio of the aromatic amine represented by the general formula (6) to the aromatic amine represented by the general formula (7) may be 100.0: 0. Alternatively, the mass ratio of the naphthol compound represented by General Formula (4) and the naphthol compound represented by Formula (5) may be 100.0: 0.

Furthermore, Embodiment I relates to the pigment composition produced by the above manufacturing method.

Furthermore, Embodiment I is a coloring composition containing a coloring agent, a binder resin, and an organic solvent, and relates to the coloring composition characterized in that the coloring agent contains any one of the pigment compositions. The coloring pigment composition may further contain a photopolymerizable monomer.

Furthermore, Embodiment I is an organic EL display device containing any one of the pigment compositions, a binder resin, a photopolymerizable monomer and a photopolymerization initiator, and the azo pigment represented by the general formula (1) is an azo pigment represented by the following general formula (1 '). It relates to a red coloring composition for dragons.

Formula (1 ')

However, in the general formula (1 '), X ⁹ represents a carbamoyl group or a group represented by the formula (d). R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, or -OR ⁷ . R ² to R ⁶ each independently represent a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁹ , a carbamoyl group, or an acetylamino group. R ⁷ and R ⁹ each independently represent an alkyl group having 1 to 4 carbon atoms. The red coloring composition for an organic EL display device may further contain at least one kind of pigment selected from CI pigment yellow 139 and the quinophthalone compound represented by the following general formula (2 ').

However, in the general formula (2 '), X1 to X13 are each independently a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkoxyl group that may have a substituent, an aryl group that may have a substituent, -SO ₃ H Group, -COOH group, -SO ₃ H group or -COOH group metal salt, -SO ₃ H group or -COOH group alkylammonium salt, phthalimidemethyl group which may have a substituent, or sulfamoyl group which may have a substituent Indicates. The adjacent groups of X1 to X4 and / or X10 to X13 are united to form an aromatic ring which may have a substituent.

Furthermore, Embodiment I is a color filter having a colored film formed using the red coloring composition for an organic EL display device described above, and has a peak wavelength (λ ₁ ) and a wavelength at which the emission intensity is maximized in a range of at least 430 nm to 485 nm. It has a peak wavelength (λ ₂ ) with a maximum emission intensity in the range of 560 nm to 620 nm, and the ratio (I2 / I1) of the emission intensity I1 at the wavelength λ ₁ and the emission intensity I2 at the wavelength λ ₂ is 0.4 or more and 0.9 or less. It relates to a color filter characterized in that the thickness of the colored film is less than 3.0 µm when the chromaticity coordinates in the XYZ colorimeter of the colored film measured using a white organic EL light source having an emission spectrum are x≥0.640 and 0.300≤y≤0.360.

Furthermore, Embodiment I is a color filter having a red colored film formed using the red coloring composition for an organic EL display device described above, and has a peak wavelength (λ ₁ ) and wavelength at which the emission intensity is maximized in a range of at least wavelengths 430 nm to 485 nm. It has a peak wavelength (λ ₂ ) with a maximum emission intensity in the range of 560 nm to 620 nm, and the ratio (I2 / I1) of the emission intensity I1 at the wavelength λ ₁ and the emission intensity I2 at the wavelength λ ₂ is 0.4 or more and 0.9 or less. When a white organic EL light source having spectral characteristics is used, chromaticity coordinates of the red colored film, the green colored film, and the blue colored film in the XYZ color system are (xR, yR), (xG, yG) and (xB, yB), respectively. Color filter, characterized in that the area of the triangle surrounded by these three points is 75% or more with respect to the area surrounded by red (0.67, 0.33), green (0.21, 0.71) and blue (0.14, 0.08). It is about.

Furthermore, Embodiment I relates to a color filter having a filter segment formed of the coloring composition on a substrate.

Moreover, Embodiment II of this invention is the pigment composition containing the azo pigment represented with the following general formula (1 ''), and the azo pigment represented with the following general formula (2 '') or the following general formula (3 ''). As, it relates to a pigment composition having an azo pigment represented by the general formula (1 '') and azo pigment represented by the general formula (2 '') or the general formula (3 '') is 60.0: 40.0 ~ 95.0: 5.0 .

In general formula (1 ''), A represents a hydrogen atom, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁷ or -COOR ⁸ . R ² to R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁹ , -COOR ¹⁰ , -CONHR ¹¹ , -NHCOR ¹² or- SO ₂ NHR ¹³ . R ⁷ to R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In general formula (2 ''), A each independently represents a hydrogen atom, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁷ or -COOR ⁸ . Each of R ⁷ to R ⁸ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

In general formula (3 ''), R ¹⁴ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁷ or -COOR ⁸ . R ² to R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁹ , -COOR ¹⁰ , -CONHR ¹¹ , -NHCOR ¹² or- SO ₂ NHR ¹³ . R ⁷ to R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

It is preferable that R ² is a chlorine atom and R ⁵ is a trifluoromethyl group. It is preferable that A is a phenyl group which may have a substituent.

In addition, in Embodiment II, a coupler component having a mass ratio of a naphthol compound represented by the following general formula (4 '') and a naphthol compound represented by the following general formula (5 '') is 60.0: 40.0 to 100.0: 0, and the following general formula ( An aromatic amine represented by 6 '') and an aromatic amine represented by the following general formula (7 '') have a mass ratio of 60.0: 40.0 to 100.0: 0 to react the diazo compound of the aromatic amine, and the above formula (1 '' ), (2 '') and (3 ''). However, the case where the mass ratio of the diazo compound of the coupler component and the aromatic amine is both 100.0: 0 is excluded.

In the general formula (4 ''), R ² to R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁹ , -COOR ¹⁰ , -CONHR ¹¹ , -NHCOR ¹² or -SO ₂ NHR ¹³ . In general formula (6 ''), A each independently represents a hydrogen atom, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁷ or -COOR ⁸ . In general formula (7 ''), R ¹⁴ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁷ or -COOR ⁸ . R ⁷ to R ¹³ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.

The mass ratio of the aromatic amine represented by the general formula (6 '') and the aromatic amine represented by the general formula (7 '') may be 100.0: 0. Alternatively, the mass ratio of the naphthol compound represented by the general formula (4 '') and the naphthol compound represented by the general formula (5 '') may be 100.0: 0.

Furthermore, Embodiment II relates to the pigment composition produced by the above-described production method.

Furthermore, Embodiment II is a coloring composition containing a coloring agent, a binder resin, and an organic solvent, and relates to a coloring composition in which the coloring agent contains any one of the pigment compositions. The coloring composition may further contain a photopolymerizable monomer.

Furthermore, Embodiment II relates to a color filter comprising a filter segment formed of the coloring composition on a substrate.

According to the embodiment of the present invention, by using a specific pigment composition, it is possible to provide a color filter having excellent lightness, no foreign coating film, and good heat resistance and light resistance. In addition, it can be used in industrial fields such as coloring compositions for inkjet, printing inks, resin colorants and paints.

In addition, hereinafter, as the embodiment of the present invention, mainly the description of the embodiment I, but unless specifically stated, the description of the embodiment I can be replaced with the description of the embodiment II.

Fig. 1 shows the emission spectrum of the organic EL element EL-1 obtained in the embodiment of the present invention.

Hereinafter, embodiments of the present invention will be described in detail.

In addition, "CI" referred to below means a color index (CI).

(Pigment composition)

First, the pigment composition of this embodiment is demonstrated. The pigment composition is a pigment composition containing an azo pigment represented by the general formula (1) and at least one azo pigment selected from the general formulas (2) and (3), and the azo pigment represented by the general formula (1) The mass ratio with the azo pigment selected from General Formulas (2) and (3) is 60.0: 40.0 to 95.0: 5.0.

By using the pigment composition of the present embodiment, the brightness is improved for reasons such as a change in crystal form by using two or more kinds of azo pigments, an improvement in transparency or an improvement in dispersibility as further refinement progresses.

In the general formulas (1) to (3), examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among them, a fluorine atom or a chlorine atom is preferable, and a chlorine atom is more preferable.

Moreover, as an alkyl group, it may be linear or branched, and a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, hex And an alkyl group having 1 to 8 carbon atoms such as a silyl group, heptyl group, octyl group, and 2-ethylhexyl group. Among them, an alkyl group having 1 to 4 carbon atoms is preferable, and a methyl group or an ethyl group is more preferable.

Moreover, as a perfluoroalkyl group, it may be linear or branched, and trifluoromethyl group, pentafluoroethyl group, hexafluoropropyl group, hexafluoroisopropyl group, nonafluorobutyl group, nonafluoroiso group And perfluoroalkyl groups having 1 to 8 carbon atoms such as a butyl group. Among these, a perfluoroalkyl group having 1 to 4 carbon atoms is preferable, a trifluoromethyl group or a pentafluoroethyl group is more preferable, and a trifluoromethyl group is particularly preferable.

Moreover, as an alkoxyl group, it may be linear or branched, and a C1-C8 alkoxyl group like methoxy group, ethoxy group, propoxy group, butoxy group, tert-butoxy group, octyloxy group, tert-octyloxy group. Can be mentioned. Among them, an alkoxyl group having 1 to 4 carbon atoms is preferable, a methoxy group or an ethoxy group is more preferable, and a methoxy group is particularly preferable.

In the groups represented by the formulas (a), (c), and (d), the halogen atom, alkyl group, perfluoroalkyl group, and alkoxyl group are synonymous with the general formulas (1) to (3), and the preferred forms are also the same. . Further, n, p, and q are integers from 1 to 10, with integers from 2 to 4 being preferred and 3 being particularly preferred.

Preferred forms of the general formulas (1) to (3) include: X ¹ is a chlorine atom, X ⁴ is a trifluoromethyl group, X ⁶ is a hydrogen atom, a methyl group or a methoxy group, X ² , X ³ , X ⁵ and X ¹⁰ is a hydrogen atom. Further, as another preferable mode, in the case group X it is ^9, represented by the formula (d). When X ⁹ is a group represented by formula (d), it is preferred from the viewpoint of brightness. Moreover, when X ⁶ is a methyl group or a methoxy group, it is preferable from a viewpoint of lightness and dispersibility.

The pigment composition of the present embodiment may be a mixture of an azo pigment represented by the general formula (1) with an azo pigment selected from the general formulas (2) and (3), or their tautomers. have. Further, these pigments may be pigments having all crystal forms, or may be mixed crystals of all crystal forms called so-called polymorphs. The crystal form of these pigments can be confirmed by powder X-ray diffraction measurement or X-ray crystal structure analysis.

In the pigment composition of this embodiment, the mass ratio between the azo pigment represented by the general formula (1) and the azo pigment selected from the general formula (2) and the general formula (3) is in the range of 60.0: 40.0 to 95.0: 5.0. desirable. More preferably, it is in the range of 70.0: 30.0 to 90.0: 10.0. When the mass ratio of the general formula (1) in the pigment composition is 60 or more or 95 or less, excellent brightness can be obtained.

Specific examples of the azo pigment represented by the general formulas (1) to (3) are listed below, but the present invention is not limited to these.

In addition, in General Formulas (1 '') and (2 '') A of Embodiment II, as the "substituent" of the phenyl group which may have a substituent, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms , Cyano group, trifluoromethyl group, nitro group, hydroxyl group, carbamoyl group, N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, carboxyl group, sulfo group, carboxyl group or sulfo group And monovalent to trivalent metal salts of acidic groups (for example, sodium salt, potassium salt, aluminum salt, etc.). Therefore, specific examples of the phenyl group which may have a substituent include a phenyl group, p-methylphenyl group, 4-tert-butylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, o-trifluoromethylphenyl group, p-chlorophenyl group, p-bromophenyl group, 2,4-dichlorophenyl group, 3-carbamoylphenyl group, 2-chloro-4-carbamoylphenyl group, 2-methyl-4-carbamoylphenyl group, 2-methoxy-4-carbamoylphenyl group, 2-methoxy-4-methyl-3-sulfamoylphenyl group, 4-sulfophenyl group, 4-carboxyphenyl group, 2-methyl-4-sulfophenyl group, and the like, but are not limited thereto.

Further, with regard to A, as the "substituent" of a heterocyclic group which may have a substituent, a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, a trifluoromethyl group, a nitro group, a hydroxyl group, Monovalent to trivalent metal salts of acidic groups selected from carbamoyl groups, N-substituted carbamoyl groups, sulfamoyl groups, N-substituted sulfamoyl groups, carboxyl groups, sulfo groups, carboxyl groups or sulfo groups (e.g. sodium Salts, potassium salts, aluminum salts, and the like). In addition, "heterocycle" means that one or more heteroatoms other than carbon atoms are included in the atoms constituting the ring system, and may be a saturated ring or an unsaturated ring, or may be a monocyclic ring or a condensed ring. Therefore, as a heterocyclic ring, a pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, isoxazole ring, And isothiazole ring, triazole ring, thiadiazole ring, oxadiazole ring, quinoline ring, benzofuran ring, indole ring, morpholine ring, pyrrolidine ring, piperidine ring, tetrahydrofuran ring, and the like. Thus, a heterocyclic group means a monovalent free group derived by removing hydrogen atoms from these heterocycles. Accordingly, specific examples of the heterocyclic group which may have a substituent include 2-pyridyl group, 3-pyridyl group, 4-pyridyl group, 2-pyrroliyl group, 3-pyrrolyl group, 2-furyl group, 3-furyl group, 2- Thienyl group, 3-thienyl group, 2-imidazolyl group, 2-oxazolyl group, 2-thiazolyl group, piperidino group, 4-piperidyl group, morpholino group, 2-morpholinyl group, N-indole And reel groups, 2-indolyl groups, 2-benzofuryl groups, 2-benzothienyl groups, 2-quinolino groups, and N-carbazolyl groups.

As a preferable form of general formula (1 '')-(3 ''), A is a phenyl group which may have a substituent from a viewpoint of brightness. Formula in terms further brightness and dispersibility (1 '') and (2 '') R ¹ is 1-4C alkyl or -OR ⁷ is preferably, more preferably R ¹ is a methyl group or a methoxy group in the Do.

(Method for producing pigment composition)

The pigment composition of the present embodiment can be prepared by a coupling reaction between a diazonium salt and β-naphthol as is well known in the pigment field. At this time, the pigment composition can also be obtained by separately preparing and mixing the azo pigment represented by the general formula (1) and the azo pigment represented by the general formula (2) and / or the azo pigment represented by the general formula (3). Alternatively, as described below, a plurality of azo pigments can be simultaneously produced by using a plurality of compounds as at least one of aromatic amines (diazo components) and β-naphthols (coupler components). The latter can obtain a pigment composition that gives better brightness.

By simultaneously producing the azo pigment represented by the general formula (1) and the azo pigment represented by the general formula (2) and / or the azo pigment represented by the general formula (3), crystal growth can be inhibited to obtain fine pigment particles, thereby Transparency is improved, so brightness is improved.

First, the mixture of the aromatic amines represented by the general formula (6) (diazo component) and the aromatic amines represented by the general formula (7) (diazo component) in an acidic aqueous solution to which hydrochloric acid, sulfuric acid or acetic acid is added is nitrite, nitrite Or diazotized with nitrite esters. Thereby, the mixture of the diazonium salt represented by the following general formula (8) and the diazonium salt represented by the following general formula (9) can be obtained.

In General Formulas (8) and (9), X ⁶ to X ¹⁰ are as defined above, and X ⁻ represents an inorganic or organic anion.

Examples of the inorganic or organic anion, fluoride ion, chloride ion, bromide ion, iodide ion, perchlorate ion, hypochlorite ^{_{ion, CH 3 COO -, C 6}} H 5 COO - , and the like, and preferably a chloride ion, there may be mentioned ^a-bromide ion, CH ₃ COO.

Subsequently, a mixture of the diazonium salt represented by the general formula (8) and the diazonium salt represented by the general formula (9) is represented by β-naphthols (coupler component) represented by the general formula (4) and formula (5). The mixture with the resulting β-naphthol (coupler component) is usually reacted at 5 ° C to 70 ° C in an aqueous solvent. Subsequently, a post-treatment according to a certain method is performed to prepare a pigment composition containing the azo pigment represented by the general formula (1) and the azo pigment represented by the general formula (2) and / or the general formula (3). It is also possible to carry out a coupling reaction in the presence of a surfactant, resin, pigment derivative or inert solvent. In addition, the manufacturing method of the pigment composition of this embodiment is not limited to these methods.

The mixing ratio of the aromatic amines of the general formulas (6) and (7) used for the reaction, and the mixing ratio of the β-naphthols of the general formulas (4) and (5) are in the range of 60:40 to 100: 0, respectively. Can be set. By adjusting these mixing ratios, a pigment composition having a desired mass ratio can be obtained. However, when the mixing ratio of the aromatic amines of the general formulas (6) and (7) and the β-naphthol of the general formulas (4) and (5) are both 100: 0, they are represented by the general formula (1). The naphthol azo pigment is the only product. Therefore, when the mixing ratio of the aromatic amines of the general formulas (6) and (7) and the β-naphthol of the general formulas (4) and (5) are simultaneously 100: 0, it is not included in the present embodiment. .

In addition, in Embodiment II, the above " general formulas 4 to 9 " will be replaced with " general formulas 4 " to 9 ". The general formulas 4 '' to 7 '' are as described above, and the general formulas 8 '' to 9 '' will be described below.

In general formula (8 ''), A each independently represents a hydrogen atom, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent. R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁷ or -COOR ⁸ . In general formula (9 ''), R ¹⁴ is a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁷ Or -COOR ⁸ . Each of R ⁷ to R ⁸ independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. In general formula (8 '') and general formula (9 ''), X ^- represents an inorganic or organic anion.

(Refinement of pigment composition)

The pigment composition can be refined by a salt milling treatment or the like. The average primary particle size required by the TEM (transmission electron microscope) of the pigment composition is preferably in the range of 10 to 150 nm. If it is 10 nm or more, dispersion is easy and heat resistance is excellent. If it is 150 nm or less, the brightness, color and contrast ratio of the coating film are excellent. The optimum average primary particle diameter differs depending on the application, but when used in, for example, a color filter, the average primary particle diameter is particularly preferably in the range of 10 to 50 nm.

The salt milling treatment is a treatment of mechanically kneading a mixture of a pigment composition and a water-soluble inorganic salt and a water-soluble organic solvent while heating using a kneader, followed by washing with water to remove the water-soluble inorganic salt and the water-soluble organic solvent. As a kneading machine, a kneader, a two-roll mill, a three-roll mill, a ball mill, an writer, and a sand mill are mentioned, for example. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed using high hardness of the inorganic salt during salt milling. By optimizing the conditions at the time of salt-milling the pigment composition, it is possible to obtain a pigment composition having a very fine primary particle diameter and a narrow distribution so that a sharp particle size distribution is achieved.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate, and the like can be used, but it is preferable to use sodium chloride (salt) in terms of price. The water-soluble inorganic salt is preferably 50 to 2000 parts by weight, and most preferably 300 to 1000 parts by weight, with respect to 100 parts by weight of the pigment, in terms of treatment efficiency and production efficiency.

The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety since the temperature rises during salt milling and the solvent tends to evaporate. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether , Triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol mono Ethyl ether and liquid polypropylene glycol are used. It is preferable to use 5 to 1000 parts by weight with respect to 100 parts by weight of the water-soluble organic solvent, and most preferably 50 to 500 parts by weight.

When the pigment composition is subjected to salt milling, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like can be used. The resin used is preferably solid and water-insoluble at room temperature, and more preferably partially soluble in the organic solvent. The amount of the resin used is preferably 5 to 200 parts by weight based on 100 parts by weight of the pigment composition.

(Coloring composition)

The coloring composition of this embodiment contains a coloring agent, a binder resin, and an organic solvent, and can also contain a coloring agent other than a dispersing auxiliary agent and a coloring agent as needed. The colorant is a pigment composition containing an azo pigment represented by general formula (1) and an azo pigment represented by general formula (2) and / or general formula (3).

(Binder resin)

The binder resin contained in the colored composition of the present embodiment disperses the pigment composition, and conventionally known thermoplastic resins, thermosetting resins, and the like can be mentioned.

Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, and polyester resin , Vinyl-based resins, alkyd resins, polystyrene resins, polyamide resins, rubber-based resins, cyclized rubber-based resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene and polyimide resins.

When used for a color filter application, it is preferable that the spectral transmittance is preferably 80% or more, more preferably 95% or more in the entire wavelength range of 400 to 700 nm of the visible light region. In addition, when used in the form of an alkali developing type coloring resistor, it is preferable to use an alkali-soluble vinyl-based resin copolymerized with an acidic group-containing ethylenically unsaturated monomer. Further, in order to further improve the photosensitivity, an energy ray-curable resin having an ethylenically unsaturated active double bond may be used.

As an alkali-soluble vinyl-type resin which copolymerized the acidic group-containing ethylenically unsaturated monomer, resin which has acidic groups, such as a carboxyl group and a sulfone group, is mentioned, for example. Specifically as the alkali-soluble vinyl-based resin, an acrylic resin having an acidic group, α-olefin / (anhydride) maleic acid copolymer, styrene / styrenesulfonic acid copolymer, ethylene / (meth) acrylic acid copolymer or isobutylene / ( Maleic anhydride) and the like. Among these, from the viewpoint of heat resistance and transparency, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrenesulfonic acid copolymer is preferred, and an acrylic resin having an acidic group is more preferable.

As the energy ray-curable resin having an ethylenically unsaturated active double bond, a resin in which a polymer having a reactive substituent is reacted with a (meth) acrylic compound having a reactive substituent and / or cinnamic acid to introduce a photocrosslinkable group into the polymer is used. Can be. As a "substituent" of "polymer having a reactive substituent", a hydroxyl group, a carboxyl group, an amino group, etc. are mentioned. As a "reactive substituent" of "(meth) acrylic compound which has a reactive substituent or cinnamic acid", an isocyanate group, an aldehyde group, an epoxy group, etc. are mentioned. Examples of the "photocrosslinkable group" include a (meth) acryloyl group, a styryl group, and the like.

Moreover, what half-esterified the polymer containing an acid anhydride with the (meth) acrylic compound which has a hydroxyl group can be used. Examples of the "polymer containing an acid anhydride" include a styrene-maleic anhydride copolymer, an α-olefin-maleic anhydride copolymer, and the like. Hydroxyalkyl (meth) acrylate etc. are mentioned as "(meth) acrylic compound which has a hydroxyl group".

It is also preferable for use as a color filter to have both alkali-soluble performance and energy ray curing performance as a thermoplastic resin.

The following are mentioned as a monomer which comprises the said thermoplastic resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate , t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) ) Acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (Meth) acrylates such as (meth) acrylate or ethoxypolyethylene glycol (meth) acrylate, or (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) ) (Meth) acrylamides such as acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide or acryloylmorpholine, styrenes such as styrene or α-methylstyrene, ethyl vinyl ether , vinyl ethers such as n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether or isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate or vinyl propionate.

Or, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy- 4-methyl-3-maleimidecoumarin, 4,4'-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenyl Rendimaleimide, N, N'-1,4-phenylenedimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4- Aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidebenzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimidehexanoate, N- [4- (2-benzoimi Dazolyl) phenyl] maleimide, and N-substituted maleimides such as 9-maleimide acridine.

Examples of the thermosetting resin include epoxy resins, benzoguanamine resins, rosin-modified maleic acid resins, rosin-modified fumaric acid resins, melamine resins, urea resins and phenol resins. Among these, an epoxy resin and a melamine resin are more preferably used from the viewpoint of improving heat resistance.

The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 80,000, and more preferably in the range of 7,000 to 50,000, in order to preferably disperse the pigment composition. The number average molecular weight (Mn) is preferably in the range of 2,500 to 40,000, and the value of Mw / Mn is preferably 10 or less.

Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are in the gel permeation chromatography "HLC-8120 GPC" manufactured by Tosoh Corporation, and four separation columns are connected in series, and as a filler, they are sequentially manufactured by Tosoh Corporation " TSK-GEL SUPER H5000 "," H4000 "," H3000 "and" H2000 "are used, and the molecular weight in terms of polystyrene measured using tetrahydrofuran as the mobile phase.

When using a binder resin for color filter use, the balance of a carboxyl group, an aliphatic group, and an aromatic group may be considered. The carboxyl group acts as an alkali soluble group upon adsorption and development to the pigment composition. Aliphatic and aromatic groups act as affinity groups for the pigment composition carrier and solvent. Therefore, it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g from the viewpoint of dispersibility, developability, and durability of the pigment composition. When the acid value is 20 mgKOH / g or more, it is excellent in solubility in a developer and it is easy to form a fine pattern. If it is 300 mgKOH / g or less, an excellent fine pattern can be formed by development.

The binder resin can be used in an amount of 20 to 500% by mass based on the total mass of the pigment composition. When it is 20 mass% or more, the film forming property and the overall resistance are excellent. If it is 500% by mass or less, the pigment concentration is sufficient, and excellent color characteristics can be expressed.

(Organic solvent)

The organic solvent can be contained in the coloring composition of this embodiment. Thereby, it is easy to form a filter segment by dispersing a pigment composition sufficiently in a pigment composition carrier, and coating it on a substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 µm. The organic solvent is selected in consideration of good coatability of the colored composition, solubility of each component of the colored composition, and safety.

Examples of the organic solvent are ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4 -Dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3- Ethoxypropionic acid ethyl, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl Acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n- Propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, Isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monoterritary butyl ether, ethylene glycol mono Butyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol Dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, Cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, tria Cetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether Le, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone , Methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, and the like.

Among these, from the viewpoint of good solubility and applicability of each component of the coloring composition, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. It is preferable to use aromatic alcohols such as glycol acetates and benzyl alcohol, and ketones such as cyclohexanone.

These organic solvents may be used alone or in combination of two or more. In addition, the organic solvent is 500 to 4000% by mass based on the total mass of the pigment composition as a reference (100% by mass), since the colored composition can be adjusted to an appropriate viscosity to form a filter segment having a desired uniform film thickness. It is preferred to use in amounts.

(Distribution aid)

When dispersing the pigment composition in the pigment composition carrier, a dispersing aid such as a pigment derivative, a resin type dispersant, or a surfactant can be used as appropriate. The dispersing aid is excellent in dispersing the pigment composition and has a great effect of preventing re-agglomeration of the pigment composition after dispersion. Therefore, when a coloring composition in which a pigment composition is dispersed in a pigment composition carrier using a dispersing aid is used, a color filter having a high spectral transmittance (brightness) can be obtained.

The dispersing aid is preferably used in an amount of 0.1 to 300% by weight based on the total amount (100% by weight) of the pigment composition.

(Pigment derivative)

As a dye derivative, the compound which introduce | transduced the basic substituent, the acidic substituent, or the phthalimide methyl group which can have a substituent in the organic pigment, anthraquinone, acridon, or triazine is mentioned. For example, Japanese Patent Publication No. 63-305173, Japanese Patent Publication No. 57-15620, Japanese Patent Publication No. 59-40172, Japanese Patent Publication No. 63-17102, Japanese Patent Publication No. 5-9469 What is described in the publication, etc. can be used. These may be used alone or in combination of two or more. When a pigment derivative is used, it is preferable from the viewpoint of brightness and dispersibility to have an azo skeleton, a naphtholazo skeleton, a diketopyrrolopyrrole skeleton, an anthraquinone skeleton, a quinophthalone skeleton and a perylene skeleton.

The blending amount of the pigment derivative is preferably 0.5% by weight or more, more preferably 1% by weight or more, and most preferably 3% by weight, based on the total amount of the pigment composition (100% by weight) from the viewpoint of improving dispersibility of the pigment composition. That's it. In addition, from the viewpoint of heat resistance and light resistance, the total amount of the pigment composition is preferably 40% by weight or less, more preferably 35% by weight or less, based on (100% by weight).

(Resin type dispersant)

The resin-type dispersant has an affinity site for a pigment composition having a property adsorbed on the pigment composition, and a site compatible with the pigment composition carrier, and is adsorbed on the pigment composition to stabilize the dispersion to the pigment composition carrier. Is to do. Specifically as a resin type dispersant,

Polycarboxylic acid esters such as polyurethane and polyacrylate;

Unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid ammonium salt and long chain polyaminoamide phosphate;

Polysiloxanes, hydroxyl group-containing polycarboxylic acid esters or modified products thereof;

Oily dispersants such as amides and salts thereof formed by the reaction of poly (lower alkyleneimine) and polyesters having free carboxyl groups;

(Meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer;

Water-soluble resins such as polyvinyl alcohol and polyvinylpyrrolidone, and water-soluble polymer compounds;

As other, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide addition compounds, phosphoric acid ester-based, etc. are used,

These may be used alone or in combination of two or more, but are not necessarily limited to these.

For the reason that the viscosity of the coloring composition is low and the spectral transmittance is high in a small amount of the dispersant, a polymer dispersant having a basic functional group is preferable, a graft copolymer containing a nitrogen atom, and an acrylic block containing a nitrogen atom having a functional group in a side chain Copolymers and urethane-based polymers are preferred. As a functional group of a side chain, tertiary amino group, quaternary ammonium base, nitrogen-containing heterocycle, etc. are mentioned. The resin type dispersant is preferably used in an amount of 5 to 200% by weight relative to the total amount of the pigment composition, and more preferably in an amount of 10 to 100% by weight from the viewpoint of film formability.

As commercially available resin-type dispersants, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171 , 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, etc. 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, 48, 452, 4008 manufactured by Chiba Japan , 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550 , 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajispa-PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine Techno. Can be.

(Surfactants)

Examples of the surfactant include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkylnaphthalinesulfonate, sodium alkyldiphenyl ether disulfonate, d Anionic surfactants such as monoethanolamine uryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of a styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate ester; Nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; Cationic surfactants such as alkyl quaternary ammonium salts and ethylene oxide adducts thereof; And alkyl betaines such as alkyldimethylaminoacetic acid betaine and amphoteric surfactants such as alkylimidazoline. These may be used alone or in combination of two or more, but are not limited thereto.

The blending amount in the case of adding the resin-type dispersant and surfactant is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight, based on the total amount of the pigment composition (100% by weight). If the compounding amount of the resin-type dispersant and surfactant is 0.1% by weight or more, the added effect can be sufficiently obtained, and if the compounding amount is 55% by weight or less, the dispersibility is excellent.

(Other coloring)

In order to adjust chromaticity and the like in the coloring composition of the present embodiment, the azo pigment of the general formula (1) and the general formula (2) and the general formula (3) are selected without detracting from the effects of the present invention. A pigment or dye other than the pigment composition containing an azo pigment can also be used together.

For example, C.I. PIGMENT RED7, 14, 41, 48: 1, 48: 2, 48: 3, 48: 4, 57: 1, 81, 81: 1, 81: 2, 81: 3, 81: 4, 122, 146, 168 , 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, 278, 279 Red pigments, such as 280, 281, 282, 283, 284, 285, 286, or 287, are mentioned. As a red dye, xanthene type, azo type (pyridone type, barbituric acid type, metal complexing system, etc.), disazo type, anthraquinone type etc. are mentioned. Specifically, C.I. And salt-forming compounds of xanthene-based acid dyes such as ACID RED52, 87, 92, 289, and 338.

In addition, C.I. Orange pigments such as PIGMENT ORANGE38, 43, 71 or 73 or C.I. PIGMENT YELLOW1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37 , 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104 , 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154 , 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193 Yellow pigments such as, 194, 198, 199, 213, 214, 218, 219, 220 or 221 may be used in combination. Moreover, as an orange dye or a yellow dye, a quinoline system, an azo system (pyridone system, barbituric acid system, metal complex system, etc.), disazo system, methine system, etc. are mentioned.

Preferred dyes to be used in combination include azo-based, naphthol-azo-based, diketopyrrolopyrrole-based, anthraquinone-based, quinophthalone-based and perylene-based dyes from the viewpoint of color properties. Specifically, C.I. PIGMENT RED176, 177, 242, 254, C.I. PIGMENT YELLOW138, 139, 150, 185.

It is preferable that other pigments are in the range of 0 to 80% by weight based on 100% by weight of the total colorant. More preferably, it is in the range of 0 to 70% by weight. If the other pigment is 80% by weight or less, it is preferable because the effect of excellent brightness can be sufficiently exhibited.

(Production method of coloring composition)

The coloring composition of the present embodiment can be prepared by mixing the pigment composition with a binder resin, an organic solvent, and a dispersing aid or other pigment, if necessary, and then finely dispersing it using a dispersing means. Examples of the dispersing means include a kneader, a two-roll mill, a three-roll mill, a ball mill, a transverse sand mill, a longitudinal sand mill, an annular bead mill, or an writer. Moreover, the coloring composition of this embodiment can also disperse | distribute a pigment composition, other pigment, etc. at the same time to a pigment composition carrier, and can also mix what was disperse | distributed individually to the pigment composition carrier later.

(Photosensitive coloring composition)

The coloring composition of this embodiment can be used as a photosensitive coloring composition by further adding a photopolymerizable monomer.

(Photopolymerizable monomer)

The photopolymerizable monomer of the present embodiment includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to produce a transparent resin.

As a monomer and oligomer that is cured by ultraviolet rays or heat to produce a transparent resin, for example, methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (Meth) acrylate, cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (Meth) acrylate, tripropylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol Diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate , Dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, ester acrylate, (meth) acrylic acid ester of methylolated melamine, epoxy (meth) acrylate, various acrylic acid esters such as urethane acrylate And methacrylic acid ester, (meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acrylamide , N-vinyl formamide, acrylonitrile, and the like, but are not limited thereto.

These photopolymerizable compounds may be used alone or in combination of two or more at any ratio as necessary.

The blending amount of the photopolymerizable monomer is preferably 5 to 400 parts by weight relative to 100 parts by weight of the pigment composition, and more preferably 10 to 300 parts by weight from the viewpoint of photocurability and developability.

(Photopolymerization initiator)

To the photosensitive coloring composition of the present invention, a photopolymerization initiator can be added to realize a solvent developing type or alkali developing type photosensitive coloring composition. Thereby, this composition can be hardened by ultraviolet irradiation and a filter segment can be formed by a photolithography method.

Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl ) Methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, etc. Acetophenone-based compounds; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether or benzyl dimethyl ketal; Benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenylsulfide or 3,3 ', 4,4'-tetra (t -Benzophenone compounds such as butyl peroxycarbonyl) benzophenone; Thioxanthone-based compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone or 2,4-diethylthioxanthone ; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis ( Trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s -Triazine, 2- (4-methoxy-naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl)- Triazine-based compounds such as 6-triazine or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzoyloxime)] or O- (acetyl) -N- (1-phenyl-2-oxo-2- (4'- Oxime ester compounds such as methoxynaphthyl) ethylidene) hydroxylamine; Phosphine-based compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; Quinone compounds such as 9,10-phenanthrene quinone, campaquinone and ethyl anthraquinone; Borate compounds; Carbazole-based compounds; Imidazole-based compounds; Or a titanocene-based compound or the like is used.

These photopolymerization initiators may be used alone or in combination of two or more at any ratio if necessary.

The content of the photopolymerization initiator is preferably 2 to 200 parts by weight with respect to 100 parts by weight of the pigment composition, and more preferably 3 to 150 parts by weight from the viewpoint of photocurability and developability.

(Sensitizer)

Furthermore, a sensitizer can be contained in the photosensitive coloring composition of this embodiment.

Examples of the sensitizer include chalcone derivatives, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by benzyl or campaquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, polymethine pigments, acridine derivatives, and azine derivatives , Thiazine derivative, oxazine derivative, indoline derivative, azrene derivative, azurenium derivative, squarylium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative, tetrabenzoporphyrin derivative, tetrapyrazinonopyrazine derivative , Phthalocyanine derivatives, tetraazapolpyrazine derivatives, tetrakynokisarilopolpyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyryllium derivatives, thiopyryllium derivatives, tetrapyrine derivatives, anurene derivatives, spiropyran derivatives, spirooxazine Derivatives, Chiosupiropiran derivatives, metal arene complexes, organic ruthenium complexes or mihiraketone derivatives, α-acyloxyesters, acylphosphine oxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrenquinone, campa Quinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzophenone, 4,4'-diethylaminobenzo And phenones.

These sensitizers may be used alone or in combination of two or more at any ratio as necessary.

More specifically, editors such as Makoto Okawara, "Pigment Handbook" (1986, Codansa), editors such as Okawara Makoto, "Chemicals of Functional Pigments" (1981, CMC), Ikemori Chusaburo, etc. And sensitizers described in "Special Functional Materials" (CMC, 1986). In addition, a sensitizer that exhibits absorption for light from ultraviolet to near infrared can also be included.

The content of the sensitizer is preferably 3 to 60 parts by weight with respect to 100 parts by weight of the photopolymerization initiator contained in the photosensitive coloring composition, and more preferably 5 to 50 parts by weight from the viewpoint of photocurability and developability.

(Amine compound)

Moreover, the photosensitive coloring composition of this embodiment can contain the amine compound which has the function of reducing the dissolved oxygen.

As such an amine compound, triethanolamine, methyldiethanolamine, triisopropanolamine, 4-dimethylaminobenzoate methyl, 4-dimethylaminobenzoate ethyl, 4-dimethylaminobenzoic acid isoamyl, benzoic acid 2-dimethylaminoethyl, 4- And 2-ethylhexyl dimethylaminobenzoic acid and N, N-dimethylparatoluidine.

The amine-based compound is preferably used in an amount of 1 to 10% by weight based on the solid content in the photosensitive coloring composition.

(Leveling agent)

It is preferable to add a leveling agent to the photosensitive coloring composition of this embodiment in order to improve the leveling property of the composition on a transparent substrate. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of the dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Torre Dow Corning Corporation, BYK-333 manufactured by Big Chemical, and the like. As a specific example of the dimethylsiloxane having a polyester structure in the main chain, BYK-310, BYK-370, etc. manufactured by BICKEMICAL CO., LTD. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain may be used together. The content of the leveling agent is usually 0.003 to 0.5% by weight based on the total weight of the photosensitive coloring composition (100% by weight).

Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule. Such a leveling agent has a hydrophilic group, but has low solubility in water, and when added to a photosensitive coloring composition, has a low ability to lower its surface tension. It is useful to have good wettability for the glass plate despite the low ability to lower the surface tension. What can sufficiently suppress chargeability can be used preferably in the addition amount in which the defect of the coating film by foaming does not appear. Dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used as a leveling agent having such desirable properties. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit. Dimethylpolysiloxane may have a polyethylene oxide unit and a polypropylene oxide unit together.

In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane may be a pendant type in which the polyalkylene oxide unit is bonded in a repeating unit of dimethylpolysiloxane, or a terminal modified type bonded to the terminal of dimethylpolysiloxane, alternately with dimethylpolysiloxane It may be of a linear block copolymer type repeatedly bonded to. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Tore Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ-2207 However, it is not limited to these.

Anionic, cationic, nonionic or amphoteric surfactants may also be auxiliaryly added to the leveling agent. Surfactants may be used by mixing two or more.

Examples of anionic surfactants added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalinesulfonate, sodium alkyldiphenyletherdisulfonate , Monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, etc. Can be lifted.

Examples of the cationic surfactant to be added to the leveling agent are alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of the nonionic surfactant added to the leveling agent are polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, and polyoxyethylene sorbitan monostearate. , Amphoteric surfactants such as alkyl betaine such as polyethylene glycol monolaurate, alkyldimethylaminoacetic acid betaine, and alkylimidazoline, or fluorine-based or silicone-based surfactants.

The leveling agent is preferably used in an amount of 0.01% to 1.0% by weight based on the total amount of solids.

(Curing agent, curing accelerator)

The photosensitive coloring composition of this embodiment may contain a curing agent, a curing accelerator, and the like, as necessary, to assist curing of the thermosetting resin. As the curing agent, phenol-based resins, amine-based compounds, acid anhydrides, active esters, carbonic acid-based compounds, sulfonic acid-based compounds, and the like are effective, but are not particularly limited, and any curing agent may be used as long as it can react with a thermosetting resin. . Moreover, among these, the compound which has 2 or more phenolic hydroxyl groups in 1 molecule, and an amine-type hardener are mentioned preferably. Examples of the curing accelerator include amine compounds (eg dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl-N, N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (eg, triethylbenzylammonium chloride, etc.), block isocyanate compounds (eg, dimethylamine, etc.), imidazole derivatives bicyclic amidine compounds And salts thereof (for example, imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1 -Cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g. triphenylphosphine, etc.), guanamine Compounds (e.g. melamine, guanamin, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (e.g. 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyl Oxyethyl-S-triazine isocyanurate adduct, etc.) and the like can be used. These may be used alone or in combination of two or more. As content of the said curing agent, 0.01-15 weight part is preferable with respect to 100 weight part of thermosetting resins. The content of the curing accelerator is preferably 0.01 to 15 parts by weight with respect to 100 parts by weight of the thermosetting resin.

(Other additive components)

The photosensitive coloring composition of this embodiment can contain a storage stabilizer in order to stabilize the viscosity with time. Moreover, in order to improve the adhesiveness with a transparent substrate, you may contain the adhesion improver, such as a silane coupling agent.

As the storage stabilizer, for example, quaternary ammonium chlorides such as benzyltrimethylchloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, tetraphenylphosphine Organic phosphine, phosphite, etc. are mentioned. The storage stabilizer may be used in an amount of 0.1 to 10 parts by weight based on 100 parts by weight of the colorant.

Examples of the adhesion improving agent include vinyl silanes such as vinyl tris- (β-methoxyethoxy) silane, vinylethoxysilane, and vinyl trimethoxysilane, and (meth) acryl silane such as γ-methacryloxypropyl trimethoxysilane. , Β- (3,4-epoxycyclohexyl) ethyl trimethoxysilane, β- (3,4-epoxycyclohexyl) methyl trimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrie Epoxysilanes such as methoxysilane, β- (3,4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane, N-β (Aminoethyl) γ-aminopropyltrimethoxysilane, N-β (aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxycysilane, γ-aminopropyl Aminosilanes such as triethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltriethoxysilane, γ-mercaptopropyl And silane coupling agents such as thiosilanes such as trimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion promoter may be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, relative to 100 parts by weight of the coloring agent in the photosensitive coloring composition.

(Removal of coarse particles)

It is preferable that the coloring composition and the photosensitive coloring composition of this embodiment perform removal of coarse particles and entrained dust by means such as centrifugation, sintering filter or filtration with a membrane filter. Preferably, the coarse particles and dust of 5 µm or more, more preferably 1 µm or more, and more preferably 0.5 µm or more are removed. It is preferable that a coloring composition and a photosensitive coloring composition do not contain the particle | grains of 0.5 micrometer or more substantially. Particularly preferably, the particles are substantially 0.3 µm or less.

(Color filter)

Next, the color filter of this embodiment is demonstrated. The color filter of the present embodiment includes a red filter segment, a green filter segment, and a blue filter segment. Among them, the red filter segment is formed of a coloring composition or a photosensitive coloring composition containing the azo pigment of the present embodiment.

The green filter segment can be formed using a conventional green coloring composition or a green photosensitive coloring composition comprising a green pigment and a pigment carrier. As a green pigment, for example, C.I. PIGMENT GREEN7, 10, 36, 37, 58, etc. can be used. Moreover, blue pigments, such as aluminum phthalocyanine, can also be used.

Moreover, a yellow pigment can be used together with a green coloring composition or a green photosensitive coloring composition. As a yellow pigment which can be used together, C.I. PIGMENT YELLOW1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37 , 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104 , 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154 , 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193 , 194, 198, 199, 213, 214, 218, 219, 220 or 221. In addition, a salt-forming compound of a basic dye or an acid dye showing yellow may be used in combination.

The blue filter segment can be formed using a conventional blue coloring composition or a blue photosensitive coloring composition comprising a blue pigment and a pigment carrier. As a blue pigment, it is C.I. PIGMENT BLUE15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. Moreover, a purple pigment and a red pigment can be used together for a blue coloring composition or a blue photosensitive coloring composition. As a purple pigment that can be used in combination, C.I. And purple pigments such as PIGMENT VIOLET1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50. As a red pigment, C.I. Metal lake pigments of rhodamine-based dyes such as Pigment Red 81, 81: 1, 81: 2, 81: 3, 81: 4, and 81: 5 can be used in combination. In addition, a salt-forming compound of a basic dye or an acid dye showing blue or purple color can also be used. When a dye is used, a xanthene dye is preferred from the viewpoint of heat resistance and lightness.

In addition, this filter segment has peak wavelengths (λ ₁ ) and (λ ₂ ) at which emission intensity is maximized in a range of at least wavelengths 430 nm to 485 nm and wavelengths 560 nm to 620 nm, and emission intensity I1 at wavelength λ ₁ and When a white organic EL light source having a spectral characteristic in which the ratio of light emission intensity I2 (I2 / I1) at wavelength λ ₂ is 0.4 or more and 0.9 or less is used, color reproducibility as a color display device when each color has specific chromaticity characteristics It is preferable because it becomes high.

The ratio (I2 / I1) of the emission intensity I2 of the emission spectrum is 0.4 or more and 0.9 or less, preferably 0.5 or more and 0.8 or less, more preferably 0.5 or more and 0.7 or less, and specific chromaticity characteristics under any conditions within these ranges. By satisfying, the quality required as a color filter for an organic EL display device such as NTSC ratio can be achieved.

The color filter for an organic EL display device of the present embodiment has peak wavelengths (λ ₁ ) and (λ ₂ ) at which emission intensity is maximized in a range of at least a wavelength of 430 nm to 485 nm and a wavelength of 560 nm to 620 nm, and the wavelength λ ₁ When a white organic EL light source having a spectral characteristic in which the ratio (I2 / I1) of the luminescence intensity I1 at and the wavelength λ ₂ at (λ2 / I1) is 0.4 or more and 0.9 or less is used, the chromaticity coordinates in the XYZ colorimeter of the colored film are each (xR , yR), (xG, yG), (xB, yB), the area of the triangle surrounded by these three points is red (0.67, 0.33), green (0.21, 0.71), blue (0.14, 0.08) When it is 75% or more with respect to the area enclosed by, it is preferable because the color reproducibility as a color display device becomes high.

(Production method of color filter)

The color filter of this embodiment can be manufactured by a printing method or a photolithography method.

The formation of a filter segment by a printing method is a manufacturing method of a color filter with low cost and excellent mass production since patterning can be performed by simply printing and drying the colored composition prepared as printing ink. Furthermore, by the development of printing technology, it is possible to perform printing of fine patterns having high dimensional accuracy and smoothness. In order to perform printing, it is preferable to make the composition such that the ink does not dry or solidify on a printing plate or on a blanket. In addition, control of the fluidity of the ink on the printing press is also important, so it is also possible to adjust the ink viscosity with a dispersant or extender pigment.

When forming a filter segment by a photolithography method, the coloring composition prepared as the said solvent developing type or alkali developing type coloring resistor material can also be apply | coated so that a dry film thickness may be 0.2-5 micrometers on a transparent substrate. Application can be carried out using a spray coat, spin coat, slit coat, roll coat, or the like. If necessary, the dried film is subjected to ultraviolet exposure through a mask having a predetermined pattern provided in a contact or non-contact state. Thereafter, the uncured portion may be removed by immersion in a solvent or an alkali developer or spraying of the developer with a spray or the like. Thereby, a desired pattern can be formed. Furthermore, the same operation can be repeated for different colors to produce a color filter. Furthermore, heating may be performed as necessary to promote polymerization of the coloring resistor material. According to the photolithography method, a color filter with higher precision than the printing method can be produced.

In the development, an aqueous solution such as sodium carbonate and sodium hydroxide, or an organic alkali such as dimethylbenzylamine or triethanolamine can be used as the alkali developer. Further, an antifoaming agent or surfactant may be added to the developer. In addition, in order to increase the UV exposure sensitivity, the coloring resistor may be coated and dried, followed by coating and drying of a water-soluble or alkali-soluble resin, and forming a film to prevent polymerization inhibition by oxygen, followed by UV exposure. Examples of the resins include polyvinyl alcohol and water-soluble acrylic resins.

The color filter of the present embodiment can be produced by an electrodeposition method, a transfer method or the like in addition to the above-described methods, but the coloring composition or photosensitive coloring composition of the present embodiment can be used in any method. In addition, the electrodeposition method is a method of manufacturing a color filter by electrodepositing each color filter segment on a transparent conductive film by electrophoresis of colloidal particles using a transparent conductive film formed on a substrate. In addition, the transfer method is a method in which a filter segment is previously formed on the surface of a peelable transfer base sheet and the filter segment is transferred to a desired substrate.

Before forming each color filter segment on a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, an chromium film, a multilayer film of chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light blocking agent is dispersed is used, but is not limited to these. In addition, a thin film transistor (TFT) may be previously formed on the above-described transparent substrate or reflective substrate, and then each color filter segment may be formed. Moreover, an overcoat film, a transparent conductive film, etc. are formed on the color filter of this embodiment as needed.

<Organic EL display device>

The organic EL display device in the present embodiment includes a color filter formed of a red coloring composition containing an azo pigment represented by the general formula (1), a binder resin, a photopolymerizable monomer, and a photopolymerization initiator, and a white light-emitting organic EL device. It is preferable that it is a display device having (hereinafter referred to as "organic EL element") as a light source.

(Organic EL element (white emitting organic EL element))

The organic EL element used in the present embodiment has peak wavelengths (λ ₁ ) and (λ ₂ ) at which the emission intensity is maximized in a range of at least 430 nm to 485 nm and a wavelength of 560 nm to 620 nm, and at wavelength λ ₁ It is preferable that the ratio (I2 / I1) of the light emission intensity I1 of the light emission intensity I2 at the wavelength λ ₂ is 0.4 or more and 0.9 or less, and more preferably 0.5 or more and 0.8 or less. Especially preferably, it is 0.5 or more and 0.7 or less.

When the ratio (I2 / I1) of the emission intensity I2 has an emission spectrum of 0.4 or more and 0.9 or less, it is preferable because high brightness and wide color reproducibility can be obtained.

Furthermore, it is preferable to have a maximum value of light emission intensity or a shoulder in the range of wavelengths 530 nm to 650 nm.

The wavelength range of 430 nm to 485 nm is preferable when the color display device provided with the color filter displays blue with good color reproducibility. More preferably, it is in the range of 430 nm to 475 nm.

By using an organic EL element satisfying these configurations and the color filter, a color display device having a wide color reproduction area and high brightness can be obtained.

The light emitting layer that obtains white light emission is not particularly limited, but, for example, the following can be used. That is, the energy level of each layer of the organic EL laminated structure is defined, and light emission using tunnel injection is provided (European Patent No. 0390551), in which a white light emitting device is described as an example in a device using tunnel injection. One (Japanese Unexamined Patent Publication No. Hei 3-230584), a light emitting layer having a two-layer structure is described (Japanese Unexamined Patent Publication No. 2-220390 and Japanese Unexamined Patent Publication No. 2-216790), and a light emitting layer is divided into a plurality And composed of materials having different emission wavelengths (Japanese Unexamined Patent Publication No. 4-51491), a blue light-emitting body (fluorescence peak 380-480 nm) and a green light-emitting body (480-580 nm) laminated, further comprising a red phosphor (Japanese Unexamined Patent Publication No. Hei 6-207170), a blue light emitting layer containing a blue fluorescent dye, a green light emitting layer having a region containing a red fluorescent dye, and further comprising a green phosphor (Japanese Published Patent) Hei 7-142169).

In addition, as the light emitting material used in the present embodiment, a known material can be used as a conventional light emitting material. The compounds preferably used for red light emission from blue, green, and orange are illustrated below. However, the light emitting material is not limited to those specifically exemplified below.

Blue light emission can be obtained, for example, by using perylene, 2,5,8,11-tetra-t-butylperylene (abbreviation: TBP), 9,10-diphenylanthracene derivatives, and the like as guest materials. . In addition, styrylarylene derivatives such as 4,4'-bis (2,2-diphenylvinyl) biphenyl (abbreviation: DPVBi) and 9,10-di-2-naphthylanthracene (abbreviation: DNA), 9 It can also be obtained from anthracene derivatives such as, 10-bis (2-naphthyl) -2-tert-butylanthracene (abbreviation: t-BuDNA). In addition, polymers such as poly (9,9-dioctylfluorene) can also be used.

Green light emission includes coumarin-based pigments such as coumarin 30 and coumarin 6, bis [2- (2,4-difluorophenyl) pyridinato] picolinatoiridium (abbreviation: FIrpic), bis (2-phenyl) It can be obtained by using pyridinato) acetylacetonatoiridium (abbreviation: Ir (ppy) (acac)) as a guest material. Further, tris- (8-hydroxyquinoline) aluminum (abbreviation: Alq ₃ ), BAlq, Zn (BTZ), bis (2-methyl-8-quinolinolato) chlorogallium (abbreviation: Ga (mq) ₂ Cl ) And other metal complexes. Further, polymers such as poly (p-phenylenevinylene) can also be used.

Luminescence from orange to red is rubrene, 4- (dicyanomethylene) -2- [p- (dimethylamino) styryl] -6-methyl-4H-pyran (abbreviation: DCM1), 4- (dicyanomethylene) -2-methyl-6- (9-jurolidyl) ethynyl-4H-pyran (abbreviation: DCM2), 4- (dicyanomethylene) -2,6-bis [p- (dimethylamino) styryl]- 4H-pyran (abbreviation: BisDCM), bis [2- (2-thienyl) pyridinato] acetylacetonatoiridium (abbreviation: Ir (thp) ₂ (acac)), bis (2-phenylquinolinato) acetyl It can be obtained by using acetonatoiridium (abbreviation: Ir (pq) (acac)) or the like as a guest material. It can also be obtained from metal complexes such as bis (8-quinolinolato) zinc (abbreviation: Znq2) or bis [2-cinnamoyl-8-quinolinolato] zinc (abbreviation: Znsq2). In addition, polymers such as poly (2,5-dialkoxy-1,4-phenylenevinylene) can also be used.

As a method of forming each layer of the organic EL element used in the present embodiment: dry deposition methods such as vacuum deposition, electron beam irradiation, sputtering, plasma, and ion plating; Wet coating methods such as spin coating, dipping, flow coating, and inkjet methods; A method of depositing a luminous body on a donor film; LITI (Laser Induced Thermal Imaging) method described in Japanese Patent Publication No. 2002-534782 or S.T.Lee, et al., Proceedings of SID'02, p.784 (2002); And printing (offset printing, flexo printing, gravure printing, screen printing, inkjet printing) and the like.

It is preferable that the organic layer is a molecular deposit film. Here, the molecular deposit film is a thin film formed by depositing from a material compound in a gas phase, and a film formed by solidifying from a material compound in a solution or liquid state. Usually, this molecular deposited film can be distinguished from a thin film (molecular cumulative film) formed by the LB method by a difference in a cohesive structure, a higher order structure, or a functional difference resulting therefrom. In addition, as disclosed in Japanese Patent Laid-Open No. 57-51781, an organic layer can also be formed by dissolving a binder such as a resin and a material compound in a solvent to form a solution and then thinning it by a spin coat method or the like. The thickness of each layer is not particularly limited, but if the film thickness is too thick, a large applied voltage is required to obtain a constant light output, resulting in poor efficiency. Conversely, if the film thickness is too thin, pinholes or the like are generated, and it is difficult to obtain sufficient luminescence luminance even when an electric field is applied. Therefore, the thickness of each layer is preferably in the range of 1 μm to 1 μm, but more preferably in the range of 10 μm to 0.2 μm.

The driving method of the organic EL element used in the present embodiment can be driven not only by the passive matrix method but also by the active matrix method. Moreover, as a method of extracting light from the organic EL element of the present embodiment, it is applicable not only to the bottom emission method of extracting light from the anode side, but also to the top emission method of extracting light from the cathode side. These methods and techniques are described in Kidoji Kuji, "Everything of Organic EL", and Nippon-Jitsukyo Publishing House (published in 2003).

The main method of the full-coloring method of the organic EL element used in this embodiment is the color filter method. The color filter method is a method of extracting light of three primary colors through a color filter using an organic EL device emitting white light. In addition to these three primary colors, it is also possible to increase the luminous efficiency of the entire device by extracting some white light as it is and using it for light emission.

Further, the organic EL element used in the present embodiment may employ a micro-cavity structure. This is an organic EL device having a structure in which a light emitting layer is disposed between an anode and a cathode, and the emitted light causes multiple interferences between the anode and the cathode. Optical properties such as reflectance and transmittance of the anode and the cathode, By appropriately selecting the film thickness of the organic layer disposed between these, it is possible to control the emission wavelength extracted from the device by actively utilizing the multiple interference effect. This makes it possible to improve the emission chromaticity. The mechanism of this multiple interference effect is described in AM-LCD Digest of Technical Papers, OD-2, p.77-80 (2002) by J. Yamada et al.

Color display becomes possible by arranging side by side on a glass substrate or the like to produce an RGB color filter layer, and disposing an ITO electrode layer and a light emitting layer (backlight) produced using the organic EL element on the color filter layer. A color display device can be obtained using this technique. At this time, it is possible to realize a color display device having a high contrast ratio by controlling the flow of current during light emission with a TFT.

Example

Hereinafter, the present invention will be described based on Examples, but the present invention is not limited thereto. In addition, in the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

In addition, the average primary particle diameter of a pigment, the method of identifying an azo pigment, the weight average molecular weight (Mw) of resin, and the acid value of resin are as follows.

(Average primary particle size of pigment)

The average primary particle diameter of the pigment was measured by using a transmission electron microscope (TEM) to directly measure the size of the primary particles through an electron microscope photograph. Specifically, the minor axis diameter and the major axis diameter of the primary particles of the individual pigments were measured, and the average was used as the particle diameter of the primary particles of the pigment. Subsequently, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating a cube of the obtained particle diameter, and the volume average particle diameter was taken as the average primary particle diameter.

(Method for identifying azo pigment)

To identify the azo pigment, an autoflex III (hereinafter referred to as TOF-MS) using a MALDI mass spectrometer manufactured by Bruker Daltonics was used. The molecular ion peak of the mass spectrum obtained by the mass spectrometer and the mass number obtained by calculation were identified.

(Resin weight average molecular weight (Mw))

The weight average molecular weight (Mw) of the resin is a polystyrene conversion measured using THF as a developing solvent by using a TSKgel column (manufactured by Tosoh Corporation) and GPC equipped with an RI detector (HLC-8120 GPC manufactured by Tosoh Corporation). It is the weight average molecular weight (Mw) of.

(Resin's acid value)

80 ml of acetone and 10 ml of water are added to 0.5 to 1.0 parts of the resin solution, stirred and dissolved uniformly, and an aqueous titration solution of 0.1 mol / L KOH is used as an appropriate titration device ("COM-555" manufactured by Hiranuma Industries). Titration was performed to measure the acid value of the resin solution. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

(Method for manufacturing binder resin solution)

(Preparation of acrylic resin solution 1)

In a separable four-necked flask, 196 parts of cyclohexanone was added to a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirrer, heated to 80 ° C., and after nitrogen substitution in the reaction container, the dropping tube was opened. Through 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumyl phenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), 2 A mixture of 1.1 parts of 2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution were sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. To the resin solution synthesized above, methoxypropyl acetate was added so that the non-volatile content was 20% by mass, and the acrylic resin Solution 1 was prepared. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)

In a separable four-necked flask, 207 parts of cyclohexanone was added to a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirrer, heated to 80 ° C., and after the nitrogen was replaced in the reaction container, the dropping tube was opened. Through 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate and 2,2'-azo A mixture of 1.33 parts of bisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Subsequently, with respect to the total amount of the copolymer solution obtained, nitrogen gas was stopped, and the mixture was stirred while injecting dry air for 1 hour, and then cooled to room temperature, followed by 6.5 parts of 2-methacryloyloxyethyl isocyanate (Current MOI manufactured by Showa Denko), A mixture of 0.08 parts dibutyltin laurate and 26 parts cyclohexanone was added dropwise to 70 ° C over 3 hours. After completion of the dropwise addition, the reaction was continued for another hour to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution were sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. To the resin solution synthesized above, cyclohexanone was added so that the non-volatile content was 20% by mass, and the acrylic resin was then added. Solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

(Method of manufacturing azo pigment)

[Example 1]

(Preparation of azo pigment 1 (R-1))

66.1 parts of 3-amino-4-methoxybenzanilide was dispersed in 1027 parts of water, ice was added to adjust the temperature to 5 ° C., 108.3 parts of 35% hydrochloric acid aqueous solution was added, stirred for 1 hour, and 19.9 parts of sodium nitrite was added to 50 parts of water to adjust One aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 80.7 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide, N- [4- (2-oxo-2,3-dihydro-1H- Benzimidazol-5-yl)]-3-hydroxy-2-naphthalenecarboamide 17.6 parts and 174.0 parts of a 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.4. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours to obtain the azo pigment represented by formula (1-1) and the azo pigment represented by formula (2-1). 158 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of the azo pigments of formulas (1-1) and (2-1) was 82.1: 17.9.

Subsequently, 100 parts of the mixture of azo pigments of the formulas (1-1) and (2-1) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue) 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 1 (R-1) was obtained. The average primary particle diameter was 38 nm.

[Example 2]

(Preparation of azo pigment 2 (R-2))

A diazonium salt aqueous solution was prepared by the same operation as in Example 1. On the other hand, 90.8 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide, N- [4- (2-oxo-2,3-dihydro-1H- Benzimidazol-5-yl)]-3-hydroxy-2-naphthalenecarboamide 8.8 parts, 25% sodium hydroxide aqueous solution 174.0 parts dissolved in 1500 parts of methanol at 50 ℃ to prepare a coupler solution.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.2. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours to obtain the azo pigment represented by formula (1-1) and the azo pigment represented by formula (2-1). 155 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of the azo pigments of formulas (1-1) and (2-1) was 91.2: 8.8.

Subsequently, 100 parts of the mixture of azo pigments of the formulas (1-1) and (2-1) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue) 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day, and 97 parts of azo pigment 2 (R-2). The average primary particle diameter was 35 nm.

[Example 3]

(Preparation of azo pigment 3 (R-3))

A diazonium salt aqueous solution was prepared by the same operation as in Example 1. On the other hand, 70.6 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide, N- [4- (2-oxo-2,3-dihydro-1H- Benzimidazol-5-yl)]-3-hydroxy-2-naphthalenecarboamide 26.4 parts, and 174.0 parts of a 25% sodium hydroxide aqueous solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.2. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the azo pigment represented by formula (1-1) and the azo pigment represented by formula (2-1) were heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours. 151 parts of mixture was obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of the azo pigments of formulas (1-1) and (2-1) was 72.8: 27.2.

Subsequently, 100 parts of the mixture of azo pigments of the formulas (1-1) and (2-1) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue) 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 3 (R-3) was obtained. The average primary particle diameter was 34 nm.

[Example 4]

(Preparation of azo pigment 4 (R-4))

61.7 parts of 3-amino-4-methylbenzanilide was dispersed in 1027 parts of water, ice was added to adjust the temperature to 5 ° C, 108.3 parts of 35% aqueous hydrochloric acid solution was added, stirred for 1 hour, and 19.9 parts of sodium nitrite was added to 50 parts of water to adjust One aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 80.7 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide, N- [4- (2-oxo-2,3-dihydro-1H- Benzimidazol-5-yl)]-3-hydroxy-2-naphthalenecarboamide 17.6 parts and 174.0 parts of a 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.5. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the azo pigment represented by formula (1-2) and the azo pigment represented by formula (2-2) are heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours. 149 parts of mixture was obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of azo pigments of formulas (1-2) and (2-2) was 82.1: 17.9.

Subsequently, 100 parts of the mixture of azo pigments of the formulas (1-2) and (2-2) obtained by the above reaction, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Co., Ltd.) and 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day, and 97 parts of azo pigment 4 (R-4) was obtained. The average primary particle diameter was 36 nm.

[Example 5]

(Preparation of azo pigment 5 (R-5))

84.7 parts of the amine compound of the following formula (6-a) was dispersed in 1027 parts of water, and ice was added to adjust the temperature to 5 ° C., 108.3 parts of 35% hydrochloric acid aqueous solution was added and stirred for 1 hour, then 19.9 parts of sodium nitrite was added to 50 parts of water The adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 80.7 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide, N- [4- (2-oxo-2,3-dihydro-1H- Benzimidazol-5-yl)]-3-hydroxy-2-naphthalenecarboamide 17.6 parts and 174.0 parts of a 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.6. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours to obtain the azo pigment represented by formula (1-3) and the azo pigment represented by formula (2-3). 173 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of the azo pigments of formulas (1-3) and (2-3) was 82.1: 17.9.

Subsequently, 100 parts of the mixture of the azo pigments of the formulas (1-3) and (2-3) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Co., Ltd.), and 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 5 (R-5). The average primary particle diameter was 33 nm.

[Example 6]

(Preparation of azo pigment 6 (R-6))

79.4 parts of the amine compound of the following formula (6-b) was dispersed in 1027 parts of water, and ice was added to adjust the temperature to 5 ° C., 108.3 parts of 35% hydrochloric acid aqueous solution was added, stirred for 1 hour, and 19.9 parts of sodium nitrite was added to 50 parts of water The adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 80.7 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide, N- [4- (2-oxo-2,3-dihydro-1H- Benzimidazol-5-yl)]-3-hydroxy-2-naphthalenecarboamide 17.6 parts and 174.0 parts of a 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.5. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours. 165 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of azo pigments of formulas (1-4) and (2-4) was 82.1: 17.9.

Subsequently, 100 parts of the mixture of the azo pigments of the formulas (1-4) and (2-4) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue) Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 6 (R-6) was obtained. The average primary particle diameter was 34 nm.

[Example 7]

(Preparation of azo pigment 7 (R-7))

45.3 parts of 3-amino-4-methoxybenzamide was dispersed in 1027 parts of water, ice was added to adjust the temperature to 5 ° C, 108.3 parts of 35% hydrochloric acid aqueous solution was added, stirred for 1 hour, and 19.9 parts of sodium nitrite was added to 50 parts of water The adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 80.7 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide, N- [4- (2-oxo-2,3-dihydro-1H- Benzimidazol-5-yl)]-3-hydroxy-2-naphthalenecarboamide 17.6 parts and 174.0 parts of a 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.3. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours. 134 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of the azo pigments of formulas (1-5) and (2-5) was 82.1: 17.9.

Subsequently, 100 parts of the mixture of the azo pigments of the formulas (1-5) and (2-5) obtained by the above reaction, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue) 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day, and 97 parts of azo pigment 7 (R-7). The average primary particle diameter was 36 nm.

[Example 8]

(Preparation of azo pigment 8 (R-8))

66.4 parts of the amine compound of the following formula (6-c) was dispersed in 1027 parts of water, ice was added to adjust the temperature to 5 ° C, and 108.3 parts of 35% hydrochloric acid aqueous solution was added, stirred for 1 hour, and 19.9 parts of sodium nitrite was added to 50 parts of water The adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 80.7 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide, N- [4- (2-oxo-2,3-dihydro-1H- Benzimidazol-5-yl)]-3-hydroxy-2-naphthalenecarboamide 17.6 parts and 174.0 parts of a 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.7. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours to obtain the azo pigment represented by formula (1-6) and the azo pigment represented by formula (2-6). 155 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of azo pigments of formulas (1-6) and (2-6) was 82.1: 17.9.

Subsequently, 100 parts of the mixture of the azo pigments of formulas (1-6) and (2-6) obtained by the above reaction, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Co., Ltd.) and 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 8 (R-8). The average primary particle diameter was 37 nm.

[Example 9]

(Preparation of azo pigment 9 (R-9))

66.1 parts of 3-amino-4-methoxybenzanilide was dispersed in 1027 parts of water, ice was added to adjust the temperature to 5 ° C, and 108.3 parts of 35% hydrochloric acid aqueous solution was added, stirred for 1 hour, and 19.9 parts of sodium nitrite was added to 50 parts of water The adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 72.4 parts of N- [5-chloro-2-methoxyphenyl] -3-hydroxy-2-naphthalenecarboamide, N- [4- (2-oxo-2,3-dihydro-1H-benz Imidazol-5-yl)]-3-hydroxy-2-naphthalenecarboamide 17.6 parts, 174.0 parts of 25% sodium hydroxide aqueous solution was dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.3. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours to obtain the azo pigment represented by formula (1-7) and the azo pigment represented by formula (2-1). 143 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of azo pigments of formulas (1-7) and (2-1) was 80.4: 19.6.

Subsequently, 100 parts of the mixture of the azo pigments of the formulas (1-7) and (2-1) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Co., Ltd.) and 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, then dried at 80 ° C. for 1 day to obtain 96 parts of azo pigment. 9 (R-9). The average primary particle diameter was 35 nm.

[Example 10]

(Preparation of azo pigment 10 (R-10))

66.1 parts of 3-amino-4-methoxybenzanilide was dispersed in 1027 parts of water, ice was added to adjust the temperature to 5 ° C, and 108.3 parts of 35% hydrochloric acid aqueous solution was added, stirred for 1 hour, and 19.9 parts of sodium nitrite was added to 50 parts of water The adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 68.8 parts of N- [5-chloro-2-methylphenyl] -3-hydroxy-2-naphthalenecarboamide, N- [4- (2-oxo-2,3-dihydro-1H-benzimidazole -5-yl)]-3-hydroxy-2-naphthalenecarboamide 17.6 parts and 174.0 parts of 25% sodium hydroxide aqueous solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.4. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours to obtain the azo pigment represented by formula (1-8) and the azo pigment represented by formula (2-1). 149 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of azo pigments of formulas (1-8) and (2-1) was 79.6: 20.4.

Subsequently, 100 parts of the mixture of azo pigments of the formulas (1-8) and (2-1) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue) Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day, and 97 parts of azo pigment 10 (R-10). The average primary particle diameter was 39 nm.

[Example 11]

(Preparation of azo pigment 11 (R-11))

66.1 parts of 3-amino-4-methoxybenzanilide was dispersed in 1027 parts of water, ice was added to adjust the temperature to 5 ° C, and 108.3 parts of 35% hydrochloric acid aqueous solution was added, stirred for 1 hour, and 19.9 parts of sodium nitrite was added to 50 parts of water The adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 70.7 parts of N- [4-acetylaminophenyl] -3-hydroxy-2-naphthalenecarboamide, N- [4- (2-oxo-2,3-dihydro-1H-benzimidazole-5 -Yl)]-3-hydroxy-2-naphthalenecarboamide 17.6 parts, 25% sodium hydroxide aqueous solution 174.0 parts were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.2. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours. 142 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of the azo pigments of formulas (1-9) and (2-1) was 80.1: 19.9.

Subsequently, 100 parts of the mixture of the azo pigments of the formulas (1-9) and (2-1) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue) Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day, and 97 parts of azo pigment 11 (R-11). The average primary particle diameter was 35 nm.

[Example 12]

(Preparation of azo pigment 12 (R-12))

A mixture of 52.8 parts of 3-amino-4-methoxybenzanilide and 16.3 parts of an amine compound of the following formula (7-a) is dispersed in 1027 parts of water and adjusted to a temperature of 5 ° C by adding ice, 108.3 parts of 35% aqueous hydrochloric acid solution After stirring for 1 hour, 19.9 parts of sodium nitrite was added to 50 parts of water, and an adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 100.9 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide and 174.0 parts of 25% sodium hydroxide aqueous solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution. It was prepared.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.3. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours to obtain the azo pigment represented by formula (1-1) and the azo pigment represented by formula (3-1) 154 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of azo pigments of formulas (1-1) and (3-1) was 76.5: 23.5.

Subsequently, 100 parts of the mixture of azo pigments of the formulas (1-1) and (3-1) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day, and 97 parts of azo pigment 12 (R-12). The average primary particle diameter was 34 nm.

[Example 13]

(Preparation of azo pigment 13 (R-13))

A mixture of 59.5 parts of 3-amino-4-methoxybenzanilide and 8.1 parts of the amine compound of formula (7-a) was dispersed in 1027 parts of water, adjusted to a temperature of 5 ° C by adding ice, and 108.3 parts of 35% aqueous hydrochloric acid solution was added. After stirring for 1 hour, 19.9 parts of sodium nitrite was added to 50 parts of water, and an adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. Meanwhile, a coupler solution was prepared in the same manner as in Example 12.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.2. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours to obtain the azo pigment represented by formula (1-1) and the azo pigment represented by formula (3-1) 156 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of the azo pigments of formulas (1-1) and (3-1) was 87.9: 12.1.

Subsequently, 100 parts of the mixture of azo pigments of the formulas (1-1) and (3-1) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day, and 97 parts of azo pigment 13 (R-13). The average primary particle diameter was 36 nm.

[Example 14]

(Preparation of azo pigment 14 (R-14))

A mixture of 46.3 parts of 3-amino-4-methoxybenzanilide and 24.4 parts of an amine compound of formula (7-a) is dispersed in 1027 parts of water, adjusted to a temperature of 5 ° C by adding ice, and 108.3 parts of 35% aqueous hydrochloric acid solution is added. After stirring for 1 hour, 19.9 parts of sodium nitrite was added to 50 parts of water, and an adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. Meanwhile, a coupler solution was prepared in the same manner as in Example 12.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.4. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours to obtain the azo pigment represented by formula (1-1) and the azo pigment represented by formula (3-1) 153 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of the azo pigments of formulas (1-1) and (3-1) was 65.5: 34.5.

Subsequently, 100 parts of the mixture of azo pigments of the formulas (1-1) and (3-1) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 14 (R-14). The average primary particle diameter was 38 nm.

[Example 15]

(Preparation of azo pigment 15 (R-15))

A mixture of 49.4 parts of 3-amino-4-methylbenzanilide and 15.4 parts of the amine compound of the following formula (7-b) was dispersed in 1027 parts of water, adjusted to a temperature of 5 ° C by adding ice, and 108.3 parts of 35% aqueous hydrochloric acid solution was added. After stirring for 1 hour, 19.9 parts of sodium nitrite was added to 50 parts of water, and an adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 100.9 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide and 174.0 parts of 25% sodium hydroxide aqueous solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution. It was prepared.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.4. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours. 151 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of azo pigments of formulas (1-2) and (3-2) was 76.3: 23.7.

Subsequently, 100 parts of a mixture of the azo pigments of the formulas (1-2) and (3-2) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Co., Ltd.), and 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 15 (R-15). The average primary particle diameter was 39 nm.

[Example 16]

(Preparation of azo pigment 16 (R-16))

A mixture of 67.8 parts of the amine compound of formula (6-a) and 16.3 parts of the amine compound of formula (7-a) was dispersed in 1027 parts of water, adjusted to a temperature of 5 ° C by adding ice, and 108.3 parts of 35% hydrochloric acid aqueous solution was added to 1 After stirring for 1 hour, 19.9 parts of sodium nitrite was added to 50 parts of water, and an adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 100.9 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide and 174.0 parts of 25% sodium hydroxide aqueous solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution. It was prepared.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.5. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours. 169 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of the azo pigments of formulas (1-3) and (3-1) was 80.7: 19.3.

Subsequently, 100 parts of the mixture of the azo pigments of the formulas (1-3) and (3-1) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue) 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, then dried at 80 ° C. for 1 day to obtain 96 parts of azo pigment. 16 (R-16). The average primary particle diameter was 33 nm.

[Example 17]

(Preparation of azo pigment 17 (R-17))

A mixture of 63.5 parts of the amine compound of formula (6-b) and 16.3 parts of the amine compound of formula (7-a) was dispersed in 1027 parts of water, adjusted to a temperature of 5 ° C by adding ice, and 108.3 parts of 35% hydrochloric acid aqueous solution was added to 1 After stirring for 1 hour, 19.9 parts of sodium nitrite was added to 50 parts of water, and an adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 100.9 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide and 174.0 parts of 25% sodium hydroxide aqueous solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution. It was prepared.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.3. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours. 164 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of azo pigments of formulas (1-4) and (3-1) was 79.6: 20.4.

Subsequently, 100 parts of the mixture of azo pigments of formulas (1-4) and (3-1) obtained by the above reaction, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Co., Ltd.). It was kneaded at 60 ° C. for 6 hours and subjected to salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day, and 97 parts of azo pigment 17 (R-17). The average primary particle diameter was 39 nm.

[Example 18]

(Preparation of azo pigment 18 (R-18))

A mixture of 36.3 parts of 3-amino-4-methoxybenzamide and 16.3 parts of an amine compound of formula (7-a) was dispersed in 1027 parts of water, adjusted to a temperature of 5 ° C by adding ice, and 108.3 parts of 35% aqueous hydrochloric acid solution was added. After stirring for 1 hour, 19.9 parts of sodium nitrite was added to 50 parts of water, and an adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 100.9 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide and 174.0 parts of 25% sodium hydroxide aqueous solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution. It was prepared.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.4. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours. 139 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of the azo pigments of formulas (1-5) and (3-1) was 69.1: 30.9.

Subsequently, 100 parts of the mixture of azo pigments of the formulas (1-5) and (3-1) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue) 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, then dried at 80 ° C. for 1 day to obtain 96 parts of azo pigment. 18 (R-18). The average primary particle diameter was 33 nm.

[Example 19]

(Preparation of azo pigment 19 (R-19))

A mixture of 53.1 parts of the amine compound of formula (6-c) and 16.3 parts of the amine compound of formula (7-a) was dispersed in 1027 parts of water, adjusted to a temperature of 5 ° C by adding ice, and 108.3 parts of 35% hydrochloric acid aqueous solution was added to 1 After stirring for 1 hour, 19.9 parts of sodium nitrite was added to 50 parts of water, and an adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 100.9 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide and 174.0 parts of 25% sodium hydroxide aqueous solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution. It was prepared.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.8. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours to obtain the azo pigment represented by formula (1-6) and the azo pigment represented by formula (3-1). 154 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of azo pigments of formulas (1-6) and (3-1) was 76.5: 23.5.

Subsequently, 100 parts of the mixture of azo pigments of the formulas (1-6) and (3-1) obtained by the above reaction, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue) 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day, and 97 parts of azo pigment 19 (R-19). The average primary particle diameter was 35 nm.

[Example 20]

(Preparation of azo pigment 20 (R-20))

A mixture of 52.9 parts of 3-amino-4-methoxybenzanilide and 16.3 parts of amine compound of formula (7-a) was dispersed in 1027 parts of water and adjusted to a temperature of 5 ° C by adding ice, and 108.3 parts of 35% aqueous hydrochloric acid solution was added. After stirring for 1 hour, 19.9 parts of sodium nitrite was added to 50 parts of water, and an adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 90.4 parts of N- [5-chloro-2-methoxyphenyl] -3-hydroxy-2-naphthalenecarboamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution. Did.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.3. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours to obtain the azo pigment represented by formula (1-7) and the azo pigment represented by formula (3-3). 144 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of azo pigments of formulas (1-7) and (3-3) was 80.3: 19.7.

Subsequently, 100 parts of the mixture of the azo pigments of the formulas (1-7) and (3-3) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue) Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 20 (R-20). The average primary particle diameter was 35 nm.

[Example 21]

(Preparation of azo pigment 21 (R-21))

A mixture of 52.9 parts of 3-amino-4-methoxybenzanilide and 16.3 parts of amine compound of formula (7-a) was dispersed in 1027 parts of water and adjusted to a temperature of 5 ° C by adding ice, and 108.3 parts of 35% aqueous hydrochloric acid solution was added. After stirring for 1 hour, 19.9 parts of sodium nitrite was added to 50 parts of water, and an adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, a coupler solution was prepared by dissolving 86.4 parts of N- [5-chloro-2-methylphenyl] -3-hydroxy-2-naphthalenecarboamide and 174.0 parts of 25% sodium hydroxide aqueous solution at 1500 ° C in methanol at 50 ° C.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.4. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours to obtain the azo pigment represented by formula (1-8) and the azo pigment represented by formula (3-4). 138 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of the azo pigments of formulas (1-8) and (3-4) was 80.3: 19.7.

Subsequently, 100 parts of the mixture of the azo pigments of the formulas (1-8) and (3-4) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue) 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for one day to obtain 95 parts of azo pigment. 21 (R-21). The average primary particle diameter was 34 nm.

[Example 22]

(Preparation of azo pigment 22 (R-22))

A mixture of 52.9 parts of 3-amino-4-methoxybenzanilide and 16.3 parts of amine compound of formula (7-a) was dispersed in 1027 parts of water and adjusted to a temperature of 5 ° C by adding ice, and 108.3 parts of 35% aqueous hydrochloric acid solution was added. After stirring for 1 hour, 19.9 parts of sodium nitrite was added to 50 parts of water, and an adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, a coupler solution was prepared by dissolving 88.4 parts of N- [4-acetylaminophenyl] -3-hydroxy-2-naphthalenecarboamide and 174.0 parts of 25% sodium hydroxide aqueous solution in 1500 parts of methanol at 50 ° C.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.3. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours. 141 parts of the mixture were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of azo pigments of formulas (1-9) and (3-5) was 80.3: 19.7.

Subsequently, 100 parts of the mixture of azo pigments of formulas (1-9) and (3-5) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Co., Ltd.) and 60 Kneading was carried out at 6 DEG C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day, and 97 parts of azo pigment 22 (R-22). The average primary particle diameter was 37 nm.

[Example 23]

(Preparation of azo pigment 23 (R-23))

A mixture of 52.9 parts of 3-amino-4-methoxybenzanilide and 16.3 parts of amine compound of formula (7-a) was dispersed in 1027 parts of water and adjusted to a temperature of 5 ° C by adding ice, and 108.3 parts of 35% aqueous hydrochloric acid solution was added. After stirring for 1 hour, 19.9 parts of sodium nitrite was added to 50 parts of water, and an adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 80.7 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide, N- [4- (2-oxo-2,3-dihydro-1H- Benzimidazol-5-yl)]-3-hydroxy-2-naphthalenecarboamide 17.6 parts and 174.0 parts of a 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of methanol at 50 ° C to prepare a coupler solution.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.1. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the azo pigment represented by formula (1-1) and the azo pigment represented by formula (2-1) were heated to 70 ° C., filtered, washed with water and dried at 90 ° C. for 24 hours. 146 parts of mixtures of azo pigments represented by formula (3-1) were obtained. As a result of mass spectrometry by TOF-MS, it was confirmed that the mass ratio of the mixture of azo pigments of formulas (1-1), (2-1), and (3-1) was 65.6: 14.3: 20.1.

Subsequently, 100 parts of the mixture of the azo pigments of the formulas (1-1) and (2-1) and (3-1) obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were made from stainless steel 1 gallon kneader ( Inoue Manufacturing Co., Ltd.), and kneaded at 60 ° C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for one day to obtain 95 parts of azo pigment. 23 (R-23). The average primary particle diameter was 34 nm.

[Example 24]

(Preparation of azo pigment 24 (R-24))

66.1 parts of 3-amino-4-methoxybenzanilide was dispersed in 1027 parts of water, ice was added to adjust the temperature to 5 ° C, and 108.3 parts of 35% hydrochloric acid aqueous solution was added, stirred for 1 hour, and 19.9 parts of sodium nitrite was added to 50 parts of water The adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 100.9 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C to prepare a coupler solution. It was prepared.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.3. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C, filtered, washed with water and dried at 90 ° C for 24 hours to obtain 158 parts of azo pigment represented by formula (1-1). It identified that it was an azo pigment of Formula (1-1) as a result of the mass spectrometry by TOF-MS.

Subsequently, 66.1 parts of 3-amino-4-methoxybenzanilide was dispersed in 1027 parts of water, ice was added to adjust the temperature to 5 ° C, and 108.3 parts of 35% hydrochloric acid aqueous solution was added and stirred for 1 hour, and 19.9 parts of sodium nitrite was added to 50 parts of water. The adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 88.0 parts of N- [4- (2-oxo-2,3-dihydro-1H-benzimidazol-5-yl)]-3-hydroxy-2-naphthalenecarboamide, 25% aqueous sodium hydroxide solution A coupler solution was prepared by dissolving 174.0 parts in 1500 parts of water at 50 ° C.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.2. After stirring for 3 hours and confirming the disappearance of the diazonium salt, it was heated to 70 ° C, filtered, washed with water and dried at 90 ° C for 24 hours to obtain 143 parts of the azo pigment represented by formula (2-1). It identified that it was an azo pigment of Formula (2-1) as a result of the mass spectrometry by TOF-MS.

Subsequently, 82.1 parts of azo pigments of formula (1-1), 17.9 parts of azo pigments of formula (2-1), 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) at 6 ° C. Kneading was performed for salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 24 (R-24) was obtained. The average primary particle diameter was 37 nm.

(Other manufacturing method of red pigment)

[Production Example 1]

(Preparation of red pigment 1 (RC-1))

100 parts of commercially available CI pigment red 254 (PR254) ("Irgaphor red B-CF" manufactured by Chivas Specialty Chemicals), 1200 parts of sodium chloride and 120 parts of diethylene glycol are made of stainless steel 1 gallon kneader (manufactured by Inoue Co., Ltd.) ) And kneaded at 60 ° C for 6 hours to perform salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day to 98 parts of red pigment 1 (RC-1). The average primary particle diameter was 33 nm.

[Production Example 2]

(Preparation of red pigment 2 (RC-2))

CI Pigment Red 254 ("Irgafo Red B-CF" manufactured by Chiba Specialty Chemicals) was changed to CI Pigment Red 177 (PR177) ("CROMOPHTAL RED A2B" manufactured by BASF), except for red pigment 1 ( 97 parts of red pigment 2 (RC-2) were obtained in the same manner as in the preparation of RC-1). The average primary particle diameter was 37 nm.

[Production Example 3]

(Preparation of red pigment 3 (RC-3))

CI Pigment Red 254 ("Irgafo Red B-CF" manufactured by Chivas Specialty Chemicals) and red pigment 1 (except that CI Pigment Red 176 (PR176) ("Novoperm Carmine HF3C" manufactured by Clariant) was changed. 98 parts of red pigment 3 (RC-3) were obtained in the same manner as in the preparation of RC-1). The average primary particle diameter was 35 nm.

[Production Example 4]

(Preparation of red pigment 4 (RC-4))

Red Pigment 1 (RC), except that CI Pigment Red 254 ("Irgafo Red B-CF" manufactured by Chivas Specialty Chemicals) was changed to CI Pigment Orange 38 (PO38) ("Novoperm Red HFG" manufactured by Client). -1) was performed in the same manner as in Preparation to obtain 97 parts of Red Pigment 4 (RC-4). The average primary particle diameter was 39 nm.

[Production Example 5]

(Preparation of red pigment 5 (RC-5))

Disperse 43.5 parts of 3-amino-4-methoxybenzanilide in 900 parts of water, add ice, adjust the temperature to 5 ° C, add 104.0 parts of 35% aqueous hydrochloric acid solution, stir for 1 hour, add 19.9 parts of sodium nitrite to 50 parts of water The adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 100.9 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C to prepare a coupler solution. It was prepared.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.3. After stirring for 3 hours and confirming the disappearance of the diazonium salt, it was heated to 70 ° C, filtered, washed with water and dried at 90 ° C for 24 hours to obtain 128 parts of the azo pigment represented by formula (1-1). It identified that it was an azo pigment of Formula (1-1) as a result of the mass spectrometry by TOF-MS.

Subsequently, 100 parts of azo pigment of formula (1-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 6 hours to perform salt milling treatment. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day to 98 parts of red pigment 5 (RC-5). The average primary particle diameter was 37 nm.

[Production Example 6]

(Preparation of red pigment 6 (RC-6))

29.8 parts of 3-amino-4-methoxybenzamide was dispersed in 900 parts of water, ice was added to adjust the temperature to 5 ° C., 104.0 parts of 35% aqueous hydrochloric acid solution was added, stirred for 1 hour, and 19.9 parts of sodium nitrite was added to 50 parts of water. The adjusted aqueous solution was added and stirred for 3 hours. After dispersing excess sodium nitrite by adding 3.2 parts of sulfamic acid, an aqueous diazonium salt solution was prepared by adding an aqueous solution consisting of 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% aqueous sodium hydroxide solution, and 180 parts of water. On the other hand, 100.9 parts of N- [2-chloro-5-trifluoromethylphenyl] -3-hydroxy-2-naphthalenecarboamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C to prepare a coupler solution. It was prepared.

The coupling reaction was performed by injecting the coupler solution in the aqueous diazonium salt solution at 5 ° C. for 30 minutes. The pH at this time was 4.4. After stirring for 3 hours and confirming the disappearance of the diazonium salt, it was heated to 70 ° C, filtered, washed with water and dried at 90 ° C for 24 hours to obtain 115 parts of the azo pigment represented by formula (1-5). It identified that it was an azo pigment of Formula (1-5) as a result of mass spectrometry by TOF-MS.

Subsequently, 100 parts of azo pigment of formula (1-5), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 6 hours to perform salt milling treatment. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day to 98 parts of red pigment 6 (RC-6). The average primary particle diameter was 35 nm.

(Production method of coloring composition)

[Example 25]

(Production of Coloring Composition 1 (RP-1))

After stirring and mixing the mixture of the following composition to be homogeneous, after dispersing for 5 hours in an Eiger mill ("Mini Model M-250 MK II" manufactured by Eger Japan) using a diameter of 0.5 mm zirconium oxide beads , Filtered with a filter of 5.0㎛ to prepare a colored composition 1 (RP-1).

Azo Pigment 1 (R-1) 10.0 parts

Resin type dispersant (Ajinomoto Fine Techno Corporation "PB821") 3.0 parts

Acrylic resin solution 1 35.0 parts

Propylene glycol monomethyl ether acetate 52.0 parts

[Examples 26 to 48, Comparative Examples 1 to 6]

(Production of coloring composition 2-30 (RP-2-30))

Coloring composition 1 (RP-1) except that azo pigment 1 (R-1) was changed to azo pigment 2 to 24 (R-2 to 24) and red pigment 1 to 6 (RC-1 to 6). In the same manner, coloring compositions 2 to 30 (RP-2 to 30) were prepared, respectively.

(Evaluation of coating film of coloring composition)

Evaluation of heat resistance, light resistance, and foreign matter of the coating films produced using the obtained coloring compositions (RP-1 to 30) was performed by the following method. In addition, initial viscosity evaluation of the coloring composition (RP-1 to 30) was also performed. Table 1 shows the evaluation results.

(Evaluation of heat resistance)

The colored compositions (RP-1 to 30) were applied to a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm, respectively, using a spin coater so that the dry film thickness was 2.0 μm, and then dried at 70 ° C. for 20 minutes, and then 230 A coated film substrate was produced by heating and cooling at 60 ° C. for 60 minutes. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film at the C light source was measured using a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). Furthermore, after that, as a heat resistance test, the chromaticity ([L * (2), a * (2), b * (2)]) of a C light source was measured by heating at 250 ° C. for 1 hour, and the color difference ΔEab was calculated by the following calculation formula. * Was obtained and evaluated in the following three steps.

ΔEab * = ((L * (2)-L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² ) ^{1 /2}

○: ΔEab * is less than 2.5 (good)

Δ: ΔEab * is 2.5 or more and less than 5.0 (poor)

×: ΔEab * is 5.0 or more (very bad)

(Evaluation of light resistance)

A coating film substrate was prepared in the same manner as the heat resistance evaluation, and the chromaticity ([L * (1), a * (1), b * (1)]) of the C light source was measured by a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.) ). Subsequently, an ultraviolet cut filter ("COLORED OPTICAL GLASS L38" manufactured by Hoya Co., Ltd.) was applied on the substrate, and light was irradiated for 100 hours using a 470W / m ² xenon lamp, and then chromaticity at the C light source ([L * (2) , a * (2), b * (2)]) were measured, and the color difference ΔEab * was obtained by the above calculation formula, and evaluated based on the same criteria as in the case of heat resistance.

(Evaluation of foreign substances on the coating)

The colored compositions (RP-1 to 30) were applied to a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm, respectively, using a spin coater so that the dry film thickness was 2.0 μm, and then dried at 70 ° C. for 20 minutes, and then continued to 230 ° C. The coated film substrate was produced by heating and cooling for 60 minutes with a furnace. The evaluation was performed by observation of a surface using a metal microscope “BX60” manufactured by Olympus Systems. The magnification was set to 500 times, and the number of particles observable in any 5 fields of view through the transmission was counted. It was evaluated in three steps.

○: Less than 10 foreign objects (good)

△: The number of foreign substances is 10 or more and less than 60 (bad)

×: the number of foreign matter is 60 or more (very poor)

(Initial viscosity evaluation)

As for the viscosity of the coloring composition, the viscosity (initial viscosity) at 20 rpm was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo) at 25 ° C immediately after adjusting the coloring composition. It was evaluated in three steps.

○: less than 20.0 [mPa · s] (good)

△: 20.0 or more to less than 40.0 [mPa · s] (poor)

×: 40.0 or more [mPa · s] (very poor)

As shown in Table 1, the coloring composition using the azo pigment of the present invention showed good results in heat resistance, light resistance, coating foreign matter and initial viscosity of the coating film.

(Production method of photosensitive coloring composition)

[Example 49]

(Production of photosensitive coloring composition 1 (RR-1))

After stirring and mixing the mixture of the following composition to be uniform, it was filtered through a filter of 1 μm to prepare a photosensitive coloring composition 1 (RR-1).

Coloring Composition 1 (RP-1) 15.4 parts

Coloring composition 25 (RP-25) 27.6 parts

Acrylic resin solution 2 8.2 parts

2.8 parts of photopolymerizable monomer ("Aronix M402" manufactured by Toagosei)

Photopolymerization initiator ("Irgacure 907" manufactured by Chiba Japan) 2.0 copies

Sensitizer (Hodogaya Chemical Co., Ltd. "EAB-F") 0.4 copies

Propylene glycol monomethyl ether acetate 43.6 parts

[Examples 50 to 72, Comparative Examples 7 to 11]

(Photosensitive coloring composition 2 to 29 (RR-2 to 29))

The same as in Example 49, except that the coloring composition 1 (RP-1) and the coloring composition 25 (RP-25) were changed to the combination and proportion (the proportion within the total amount of 43 parts of the coloring composition) shown in Table 2. The photosensitive coloring compositions 2 to 29 (RR-2 to 29) were obtained respectively. In addition, about the ratio change, it was made to match the chromaticity of x = 0.640 and y = 0.330 in C light source at the time of evaluation of a coating film.

(Evaluation of coating film of photosensitive coloring composition)

Evaluation of the brightness (color characteristics) of the coating films produced using the obtained photosensitive coloring compositions 1 to 29 (RR-1 to 29) was performed by the following method. Table 2 shows the evaluation results.

(Evaluation of brightness)

The photosensitive coloring compositions 1 to 29 (RR-1 to 29) were applied onto a glass substrate having a thickness of 100 mm × 100 mm and 1.1 mm, respectively, using a spin coater, and then dried at 70 ° C. for 20 minutes, and accumulated using an ultra-high pressure mercury lamp. UV exposure was performed at a light amount of 150 mJ / cm ² and development was performed with an alkaline developer at 23 ° C. to obtain a coated film substrate. Subsequently, after heating and cooling at 230 ° C. for 60 minutes, the brightness Y (C) of the obtained coating film substrate was measured using a microscopic spectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The produced coating film substrate was set to a film thickness that can be x = 0.640 and y = 0.330 in the C light source after heat treatment at 230 ° C. As the alkali developer, one composed of 1.5% by mass of sodium carbonate, 0.5% by mass of sodium hydrogen carbonate, 8.0% by mass of anionic surfactant ("Pelex NBL" manufactured by Kao Corporation), and 90% by mass of water was used. With regard to the brightness Y (C), it can be said that there is clearly a difference if it is 0.1 points or more.

(Contrast ratio evaluation)

Light emitted from the backlight unit for a liquid crystal display passes through a polarizing plate to be polarized, and passes through a coating film of a colored composition applied on a glass substrate to reach another polarizing plate. At this time, if the polarizing plate and the polarizing plane of the polarizing plate are parallel, light passes through the polarizing plate, but if the polarizing plane is orthogonal, the light is blocked by the polarizing plate. However, when light polarized by the polarizing plate passes through the coating film of the coloring composition, scattering and the like occur due to the particles of the coloring agent, and if a deviation occurs in a part of the polarizing surface, when the polarizing plate is parallel, the amount of transmitted light decreases, and when the polarizing plate is orthogonal Some light is transmitted. The transmitted light was measured as the luminance on the polarizing plate, and the ratio between the luminance at the time of parallel and the luminance at the time of orthogonality of the polarizing plate was calculated as a contrast ratio.

(Contrast ratio) = (brightness in parallel) / (brightness in orthogonal)

Therefore, when scattering occurs by the colorant in the coating film, the luminance at the time of parallel decreases and the luminance at the time of orthogonality increases, so that the contrast ratio is lowered.

In addition, a color luminance meter ("BM-5 A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. At the time of measurement, a measurement was performed through a black mask with a square hole having a length of 1 cm on one side. As the board | substrate, the thing similar to the thing which performed brightness evaluation was used.

From the results of Table 2, it was apparent that the brightness of the example using the azo pigment of this embodiment in forming the color filter was excellent. The effect of improving the brightness was confirmed by using instead of CI pigment red 177 or CI pigment red 176 which was conventionally used as a blue pigment.

(Production of color filters)

The green photosensitive coloring composition and blue photosensitive coloring composition used for the production of a color filter were prepared. In addition, for red, the photosensitive coloring composition 1 (RR-1) of the present invention was used.

(Preparation of green coloring composition 1 (GP-1))

The mixture of the composition shown below was uniformly stirred and mixed, and then dispersed for 5 hours with agar mill ("mini-model M-250 MK II" manufactured by Ager Japan) using a diameter of 0.5 mm zirconium oxide beads, and then 5.0 µm. It was filtered through a filter to prepare green coloring composition 1 (GP-1).

Green pigment (C.I. Pigment Green 36) 6.8 parts

Yellow pigment (C.I. Pigment Yellow 150) 5.2 parts

1.0 part of resin type dispersant ("EFKA4300" manufactured by Chiba Japan)

Acrylic resin solution 1 35.0 parts

Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of green photosensitive coloring composition 1 (GR-1))

After stirring and mixing the mixture of the following composition to be uniform, it was filtered through a 1 μm filter to prepare a green photosensitive coloring composition 1 (GR-1).

Green coloring composition 1 (GP-1) 42.0 parts

Acrylic resin solution 2 13.2 parts

2.8 parts of photopolymerizable monomer ("Aronix M402" manufactured by Toagosei)

Photopolymerization initiator ("Irgacure 907" manufactured by Chiba Japan) 2.0 copies

Sensitizer (Hodogaya Chemical Co., Ltd. "EAB-F") 0.4 copies

Ethylene glycol monomethyl ether acetate 39.6 parts

(Preparation of blue coloring composition 1 (BP-1))

The mixture of the composition shown below was uniformly stirred and mixed, and then dispersed for 5 hours with agar mill ("mini-model M-250 MK II" manufactured by Ager Japan) using a diameter of 0.5 mm zirconium oxide beads, and then 5.0 µm. It was filtered with a filter to prepare blue colored composition 1 (BP-1).

Blue pigment (C.I. Pigment Blue 15: 6) 7.2 parts

Purple pigment (C.I. Pigment Violet 23) 4.8 parts

1.0 part of resin type dispersant ("EFKA4300" manufactured by Chiba Japan)

Acrylic resin solution 1 35.0 parts

Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of blue photosensitive coloring composition 1 (BR-1))

The mixture of the following composition was stirred and mixed to be uniform, and then filtered through a 1 μm filter to prepare a blue photosensitive coloring composition 1 (BR-1).

Blue coloring composition 1 (BP-1) 34.0 parts

Acrylic resin solution 2 15.2 parts

3.3 parts of photopolymerizable monomer ("Aronix M400" manufactured by Toagosei)

Photopolymerization initiator ("Irgacure 907" manufactured by Chiba Japan) 2.0 copies

Sensitizer (Hodogaya Chemical Co., Ltd. "EAB-F") 0.4 copies

Ethylene glycol monomethyl ether acetate 45.1 parts

The black matrix was pattern-processed on a glass substrate, and the photosensitive coloring composition 1 (RR-1) of this invention was apply | coated on this substrate with the spin coater, and the colored coating film was formed. The coating film was irradiated with ultraviolet light of 300 mJ / cm ² using an ultra-high pressure mercury lamp through a photomask. Subsequently, spray development was performed with an alkali developer consisting of a 0.2% by weight aqueous sodium carbonate solution, and the unexposed portion was removed, washed with ion-exchanged water, and the substrate was heated to 230 ° C for 20 minutes to form a red filter segment. The formed red filter segment was x = 0.640 and y = 0.330 in the C light source. By the same method, the green filter segment, the blue filter so that the green photosensitive coloring composition 1 (GR-1) is x = 0.300, y = 0.600, and the blue photosensitive coloring composition 1 (BR-1) are x = 0.150, y = 0.060. Segments were formed to obtain color filters.

By using the photosensitive coloring composition 1 (RR-1) of the present invention, it was possible to produce a high-brightness color filter.

[Example 73]

(Preparation of azo pigment 25 (R-25))

The following formula (9) was prepared according to Example 1 of Japanese Patent Application No. 2012-254848.

The same operation as in Example 1 was carried out except that 66.1 parts of 3-amino-4-methoxybenzanilide was replaced with a mixture of 59.5 parts of 3-amino-4-methoxybenzanilide and 10.9 parts of Formula (9). 162 parts of a mixture of azo pigments represented by (1-1), formulas (2-1), (8-1), and (8-2) were obtained. As a result of mass spectrometry by TOF-MS, the mass ratio of the mixture of azo pigments of formulas (1-1), (2-1), (8-1) and (8-2) is 71.3: 16.5: 9.9 : 2.3 was confirmed.

Subsequently, 100 parts of the mixture of azo pigments obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 6 hours to perform salt milling treatment. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 25 (R-25). The average primary particle diameter was 17 nm.

[Example 74]

(Preparation of azo pigment 26 (R-26))

The following formula (10) was prepared according to Example 1 of Japanese Patent Application No. 2012-254848.

The same operation as in Example 1 was carried out, except that 66.1 parts of 3-amino-4-methoxybenzanilide was replaced with a mixture of 59.5 parts of 3-amino-4-methoxybenzanilide and 6.8 parts of Formula (10). 158 parts of a mixture of azo pigments represented by (1-1), formulas (2-1), formulas (8-7), and formulas (8-8) were obtained. As a result of mass spectrometry by TOF-MS, the mass ratio of the mixture of azo pigments of formula (1-1), formula (2-1), formula (8-7) and formula (8-8) is 73.0: 16.9: 8.2 : 1.9 was confirmed.

Subsequently, 100 parts of the mixture of azo pigments obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 6 hours to perform salt milling treatment. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 26 (R-26). The average primary particle diameter was 16 nm.

[Example 75]

(Preparation of azo pigment 27 (R-27))

The following formula (11) was prepared according to Example 8 of Japanese Patent Application No. 2012-254848.

The same operation as in Example 1 was carried out except that 66.1 parts of 3-amino-4-methoxybenzanilide was replaced with a mixture of 59.5 parts of 3-amino-4-methoxybenzanilide and 12.1 parts of Formula (11). 163 parts of a mixture of azo pigments represented by (1-1), formulas (2-1), formulas (8-9), and formulas (8-10) were obtained. As a result of mass spectrometry by TOF-MS, the mass ratio of the mixture of azo pigments of formulas (1-1), (2-1), (8-9) and (8-10) is 70.8: 16.4: 10.4 : 2.4 was confirmed.

Subsequently, 100 parts of the mixture of azo pigments obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 6 hours to perform salt milling treatment. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 27 (R-27). The average primary particle diameter was 25 nm.

[Example 76]

(Preparation of azo pigment 28 (R-28))

The following formula (12) was prepared according to Example 11 of Japanese Patent Application No. 2012-254848.

The same operation as in Example 1 was carried out except that 66.1 parts of 3-amino-4-methoxybenzanilide was replaced with a mixture of 59.5 parts of 3-amino-4-methoxybenzanilide and 12.1 parts of Formula (12). 163 parts of a mixture of azo pigments represented by (1-1), formulas (2-1), (8-11), and (8-12) were obtained. As a result of mass spectrometry by TOF-MS, the mass ratio of the mixture of azo pigments of formula (1-1), formula (2-1), formula (8-11) and formula (8-12) is 70.8: 16.4: 10.4 : 2.4 was confirmed.

Subsequently, 100 parts of the mixture of azo pigments obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 6 hours to perform salt milling treatment. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 28 (R-28). The average primary particle diameter was 28 nm.

[Example 77]

(Preparation of azo pigment 29 (R-29))

The following formula (13) was prepared according to Example 4 of Japanese Patent Application No. 2012-254848.

The same operation as in Example 1 was performed except that 66.1 parts of 3-amino-4-methoxybenzanilide was replaced with a mixture of 59.5 parts of 3-amino-4-methoxybenzanilide and 6.8 parts of Formula (13). 158 parts of a mixture of azo pigments represented by (1-1), formulas (2-1), formulas (8-13), and formulas (8-14) were obtained. As a result of mass spectrometry by TOF-MS, the mass ratio of the mixture of azo pigments of formula (1-1), formula (2-1), formula (8-13) and formula (8-14) is 73.0: 16.9: 8.2 : 1.9 was confirmed.

Subsequently, 100 parts of the mixture of azo pigments obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 6 hours to perform salt milling treatment. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 29 (R-29). The average primary particle diameter was 26 nm.

[Example 78]

(Preparation of azo pigment 30 (R-30))

The following formula (14) was prepared according to Example 3 of Japanese Patent Application No. 2012-254848.

The same operation as in Example 1 was carried out except that 66.1 parts of 3-amino-4-methoxybenzanilide was replaced with a mixture of 59.5 parts of 3-amino-4-methoxybenzanilide and 7.6 parts of Formula (14). 159 parts of a mixture of azo pigments represented by (1-1), formulas (2-1), formulas (8-15), and formulas (8-16) were obtained. As a result of mass spectrometry by TOF-MS, the mass ratio of the mixture of azo pigments of formula (1-1), formula (2-1), formula (8-15) and formula (8-16) is 72.7: 16.8: 8.6 : 1.9 was confirmed.

Subsequently, 100 parts of the mixture of azo pigments obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 6 hours to perform salt milling treatment. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 30 (R-30). The average primary particle diameter was 23 nm.

[Example 79]

(Preparation of azo pigment 31 (R-31))

The following formula (15) was prepared according to Example 147 of Japanese Patent Application No. 2012-254848.

The same operation as in Example 1 was performed except that 66.1 parts of 3-amino-4-methoxybenzanilide was replaced with a mixture of 59.5 parts of 3-amino-4-methoxybenzanilide and 17.6 parts of Formula (15). 168 parts of a mixture of azo pigments represented by (1-1), formulas (2-1), formulas (8-17), and formulas (8-18) were obtained. As a result of mass spectrometry by TOF-MS, the mass ratio of the mixture of azo pigments of formulas (1-1), (2-1), (8-17) and (8-18) is 68.6: 15.9: 12.6 It was confirmed that it was: 2.9.

Subsequently, 100 parts of the mixture of azo pigments obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 6 hours to perform salt milling treatment. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 31 (R-31). The average primary particle diameter was 21 nm.

[Example 80]

(Preparation of azo pigment 32 (R-32))

The following formula (16) was prepared according to Example 148 of Japanese Patent Application No. 2012-254848.

The same operation as in Example 1 was carried out except that 66.1 parts of 3-amino-4-methoxybenzanilide was replaced with a mixture of 59.5 parts of 3-amino-4-methoxybenzanilide and 15.1 parts of Formula (16). 166 parts of a mixture of azo pigments represented by (1-1), formulas (2-1), formulas (8-19), and formulas (8-20) were obtained. As a result of mass spectrometry by TOF-MS, the mass ratio of the mixture of azo pigments of formula (1-1), formula (2-1), formula (8-19) and formula (8-20) is 69.5: 16.1: 11.6 It was confirmed that it was: 2.8.

Subsequently, 100 parts of the mixture of azo pigments obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 6 hours to perform salt milling treatment. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 32 (R-32) was obtained. The average primary particle diameter was 16 nm.

[Example 81]

(Preparation of azo pigment 33 (R-33))

The following formula (17) was prepared according to Example 149 of Japanese Patent Application No. 2012-254848.

The same operation as in Example 1 was carried out except that 66.1 parts of 3-amino-4-methoxybenzanilide was replaced with a mixture of 59.5 parts of 3-amino-4-methoxybenzanilide and 11.7 parts of Formula (17). 163 parts of a mixture of azo pigments represented by (1-1), formulas (2-1), formulas (8-21), and formulas (8-22) were obtained. As a result of mass spectrometry by TOF-MS, the mass ratio of the mixture of azo pigments of formulas (1-1), (2-1), (8-21) and (8-22) is 70.9: 16.4: 10.3 : 2.4 was confirmed.

Subsequently, 100 parts of the mixture of azo pigments obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 6 hours to perform salt milling treatment. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 33 (R-33). The average primary particle diameter was 16 nm.

[Example 82]

(Preparation of azo pigment 34 (R-34))

The following formula (18) was prepared according to Example 150 of Japanese Patent Application No. 2012-254848.

The same operation as in Example 1 was performed except that 66.1 parts of 3-amino-4-methoxybenzanilide was replaced with a mixture of 59.5 parts of 3-amino-4-methoxybenzanilide and 11.7 parts of Formula (18). 163 parts of a mixture of azo pigments represented by (1-1), formulas (2-1), formulas (8-23), and formulas (8-24) were obtained. As a result of mass spectrometry by TOF-MS, the mass ratio of the mixture of azo pigments of formula (1-1), formula (2-1), formula (8-23) and formula (8-24) is 70.9: 16.4: 10.3 : 2.4 was confirmed.

Subsequently, 100 parts of the mixture of azo pigments obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 6 hours to perform salt milling treatment. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 34 (R-34) was obtained. The average primary particle diameter was 18 nm.

[Example 83]

(Preparation of azo pigment 35 (R-35))

The following formula (19) was prepared according to Example 151 of Japanese Patent Application No. 2012-254848.

The same operation as in Example 1 was carried out except that 66.1 parts of 3-amino-4-methoxybenzanilide was replaced with a mixture of 59.5 parts of 3-amino-4-methoxybenzanilide and 10.1 parts of Formula (19). 161 parts of a mixture of azo pigments represented by (1-1), formulas (2-1), (8-25), and (8-26) were obtained. As a result of mass spectrometry by TOF-MS, the mass ratio of the mixture of azo pigments of formulas (1-1), (2-1), (8-25) and (8-26) is 71.6: 16.6: 9.6 : 2.2 was confirmed.

Subsequently, 100 parts of the mixture of azo pigments obtained by the above reaction, 1200 parts of sodium chloride and 120 parts of diethylene glycol were placed in a 1 gallon kneader made by stainless steel (manufactured by Inoue Co., Ltd.) and kneaded at 60 ° C for 6 hours to perform salt milling treatment. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 1 day to obtain 98 parts of azo pigment. 35 (R-35). The average primary particle diameter was 25 nm.

[Examples 84 to 94]

(Production of coloring composition 31-41 (RP-31-41))

Azo pigment 1 (R-1) was changed to azo pigment 25 to 35 (R-25 to 35), except that the coloring composition 1 (RP-1) was the same as the coloring composition 31 to 41 (RP-31), respectively. ~ 41).

(Evaluation of coating film of coloring composition)

The heat resistance, light resistance, foreign material evaluation, and initial viscosity evaluation of the coating films produced using the obtained coloring compositions (RP-31 to 41) were performed by the aforementioned method. Table 3 shows the evaluation results.

As shown in Table 3, the colored composition using the azo pigment of the present invention was a good result in heat resistance, light resistance, coating foreign matter and initial viscosity of the coating film.

(Production method of photosensitive coloring composition)

[Examples 95 to 105]

(Photosensitive coloring composition 30-40 (RR-30-40))

Example 49 and except that the coloring composition 1 (RP-1) and the coloring composition 25 (RP-25) were changed to the combination and ratio (the ratio within the total 43 parts of the coloring composition) shown in Table 4 In the same manner, photosensitive coloring compositions 30 to 40 (RR-30 to 40) were obtained, respectively. In addition, about the ratio change, it was made to match the chromaticity of x = 0.640 and y = 0.330 in C light source at the time of evaluation of a coating film.

(Evaluation of coating film of photosensitive coloring composition)

Evaluation of the lightness (color characteristic) and contrast ratio of the coating film produced using the obtained photosensitive coloring composition 30-40 (RR-30-40) was performed by the method mentioned above. Table 4 shows the evaluation results.

From the results of Table 4, it was apparent that in forming the color filter, the example using the azo pigment of this embodiment was excellent in brightness. The effect of improving the brightness was confirmed by using instead of CI Pigment Red 177 and CI Pigment Red 176, which were conventionally used as blue pigments.

(Production example of organic EL element)

Hereinafter, a manufacturing example of an organic EL device used as a white light source is specifically shown. In the production example of the organic EL device, all of the mixing ratios are weight ratios unless otherwise specified. Deposition (vacuum deposition) was performed under a condition without temperature control such as heating and cooling of the substrate in a vacuum of 10 ^-6 Torr. In addition, in evaluating the luminescence properties of the device, the properties of the organic EL device having an electrode area of 2 mm x 2 mm were measured.

(Production of organic EL element 1 (EL-1))

After treating the glass plate having the cleaned ITO electrode with oxygen plasma for about 1 minute, 4, 4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl (α-NPD) was vacuum-deposited. A hole injection layer having a film thickness of 150 nm was obtained. Furthermore, on the hole injection layer, the following compound (R'-2) and compound (R'-3) were co-deposited at a composition ratio of 100: 2 to form a first light emitting layer having a thickness of 10 nm. Again, the following compound (B'-1) and compound (B'-4) were co-deposited at a composition ratio of 100: 3 to form a second light emitting layer having a thickness of 20 nm. 5 nm of α-NPD and 20 nm of the following compound (G′-3) were deposited on the emission layer again to form a third emission layer. Furthermore, a tris- (8-hydroxyquinoline) aluminum complex was vacuum deposited to form an electron injection layer having a film thickness of 35 nm, and on top of that, lithium fluoride 1 nm and then aluminum 200 nm were deposited to form an electrode to form an organic EL device 1 Got

Furthermore, in order to protect this organic EL device from the environment, it was sealed in a dry glove box filled with pure nitrogen. In this device, white light emission with a luminescence luminance of 950 (cd / m ²⁾ , a maximum emission luminance of 55000 (cd / m ² ), and a luminous efficiency of 3.9 (lm / W) was obtained at a DC voltage of 5 V. Fig. 1 shows the emission spectrum of the obtained organic EL element (EL-1).

In the range of 430 nm to 485 nm and the wavelength of 560 nm to 620 nm of the organic EL element EL-1, the peak wavelengths (λ ₁ ), (λ ₂ ) at which the emission intensity is maximized, and the emission intensity at the wavelength λ ₁ Table 5 shows the ratio (I2 / I1) of the emission intensity I2 at I1 and the wavelength lambda ₂ .

(Red colorant (PR-19))

Commercially available CI Pigment Red 254 (PR254) (BASF Corporation "Irgapo Red B-CF") 100 parts, sodium chloride 1200 parts and diethylene glycol 120 parts into a stainless steel 1 gallon kneader (manufactured by Inoue Co., Ltd.) to 60 ℃ It was kneaded for 6 hours and subjected to salt milling. The obtained kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day to 98 parts of red colorant (PR-19). The average primary particle diameter was 33 nm.

(Red colorant (PR-20))

Red Pigment Red 254 was performed in the same manner as in Preparation of Red Pigment (PR-19), except that CI Pigment Red 254 was changed to CI Pigment Red 177 (PR177) ("Chromophthaled A2B" manufactured by BASF). PR-20) 97 copies were obtained. The average primary particle diameter was 27.6 nm.

(Red colorant (PR-21))

Red Pigment Red 254 was performed in the same manner as in Preparation of Red Pigment (PR-19), except that CI Pigment Red 254 was changed to CI Pigment Red 242 (PR242) (SandorinScarlet4RF manufactured by Clariant). 21) 97 parts were obtained. The average primary particle diameter was 39 nm.

(Red colorant (PR-22))

Red pigment (PR-) was performed in the same manner as in preparation of red pigment (PR-19) except that CI pigment red 254 was changed to CI pigment red 176 (PR176) ("Novoperm Carmine HF3C" manufactured by Clariant). 22) 97 parts were obtained. The average primary particle diameter was 35 nm.

(Red colorant (PR-23))

Red pigment (PR-) was performed in the same manner as in the preparation of red pigment (PR-19) except that CI pigment red 254 was changed to CI pigment orange 38 (PO38) ("Novoperm Red HF" manufactured by Clariant). 23) 97 parts were obtained. The average primary particle diameter was 39 nm.

(Yellow colorant (PY-2))

100 parts of CI pigment Yellow 139 (PY139) ("IRGAPO Yellow 2R-CF" manufactured by BASF), 700 parts of sodium chloride and 180 parts of diethylene glycol were placed in a stainless steel 1 gallon kneader (manufactured by Inoue) and kneaded at 80 ° C for 6 hours. Ordered. This mixture was added to 2000 parts of hot water and stirred for 1 hour while heating to 80 ° C to form a slurry, and after repeated filtration and washing, the salt and solvent were removed, and then dried at 80 ° C for one day to give 95 parts of yellow colorant (PY-2 ). The average primary particle diameter was 40.2 nm.

(Yellow colorant (PY-3))

The CI Pigment Yellow 139 was changed to the CI Pigment Yellow 185 (PY185) (manufactured by BASF, "Paliogen Yellow D1155"), and the same procedure as in the preparation of the yellow colorant (PY-2) was carried out. A yellow colorant (PY-3) was obtained. The average primary particle diameter was 40.2 nm.

(Green colorant (PG-1))

Phthalocyanine Green Pigment CI Pigment Green 7 (PG7) (Toyo Color Co., Ltd. "Lionol Green YS-07") 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts stainless steel 1 gallon kneader (Inoue Co., Ltd.) ) And kneaded at 120 ° C for 4 hours. Subsequently, this kneaded material was put into 5 liters of hot water, stirred for 1 hour while heating to 70 ° C., and then filtered and washed repeatedly to remove sodium chloride and diethylene glycol, dried at 80 ° C. for 1 day to 490 parts A green colorant (PG-1) was obtained. The average primary particle diameter was 55.3 nm.

(Blue colorant (PB-1))

CI Pigment Blue 15: 6 (PB15: 6) (Toyo Color Co., Ltd. "Rionol Blue ES") 100 parts, crushed salt 800 parts and diethylene glycol 100 parts into a stainless steel 1 gallon kneader (manufactured by Inoue) 70 The mixture was kneaded at ℃ 12 hours. This mixture was added to 3000 parts of hot water and stirred for 1 hour while heating to 70 ° C to form a slurry to remove salt and solvent by repeating filtration and washing, and then dried at 80 ° C for 1 day to 98 parts of blue colorant (PB-1 ). The average primary particle diameter was 28.3 nm.

(Purple Colorant (PV-1))

CI Pigment Violet 23 (PV23) ("Fast Violet RL" manufactured by Clariant) 120 parts, 1600 parts of ground salt and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue) and kneaded at 90 ° C for 18 hours. . This mixture was added to 5000 parts of hot water and stirred for 1 hour while heating to 70 ° C to form a slurry to remove salt and solvent through filtration and washing, and then dried at 80 ° C for 1 day to 118 parts of purple colorant (PV-1 ). The average primary particle diameter was 26.4 nm.

<Production method of colorant dispersion>

(Colorant dispersion (DR-101))

After the mixture was stirred and mixed to make it uniform, the mixture was dispersed for 5 hours with an aiger mill ("mini-model M-250 MK II" manufactured by Ager Japan) using a zirconium oxide beads having a diameter of 0.5 mm, followed by filtering with a filter of 5.0 µm. Colorant dispersion (DR-101) was prepared by filtration with.

Red colorant (R-1): 12.0 parts

  (Azo pigment formula (1-1), (2-1) prepared in Example 1)

Resin type dispersant: 1.0 part

  ("EFKA4300" manufactured by Chiba Japan)

Acrylic resin solution 1: 35.0 parts

Solvent: 52.0 parts

  Propylene glycol monomethyl ether acetate (PGMAC)

(Colorant dispersion (DR-102 ~ 103, 19 ~ 23, DY-2 ~ 3, DG-1, DB-1, DV-1))

Coloring compositions (DR-102 to 103, 19 to 23) and (DY-) in the same manner as the colorant dispersion (DR-101), except that the composition (parts by weight) shown in Tables 6 and 7 was changed to a mixture. 2 to 3), (DG-1), (DB-1) and (DV-1) were prepared. In addition, the colorants "R-4" and "R-12" in Table 6 are the same as those prepared in Examples 4 and 12.

In addition, in Tables 6 and 7, EFKA4300, BYK-LPN6919 and PGMAC are as follows.

EFKA4300: manufactured by FK Chemical

BYK-LPN6919: made by Big Chemy

PGMAC: Propylene glycol monomethyl ether acetate

<Photosensitive green coloring composition, manufacturing method of photosensitive blue coloring composition>

(Photosensitive green coloring composition (RG-1))

The mixture of the following composition was stirred and mixed to be uniform, and then filtered through a 1.0 μm filter to prepare a photosensitive green colored composition (RG-1).

Colorant dispersion (DG-1): 45.1 parts

  (C.I. Pigment Green 7 (PG7))

Pigment dispersion (DY-3): 21.6 parts

  (C.I. Pigment Yellow 185 (PY185))

Acrylic resin solution 2: 4.3 parts

Photopolymerizable monomer: 4.2 parts

  ("Aronix M402" manufactured by Toagosei)

Photopolymerization initiator: 1.2 parts

  ("Irgacure 907" manufactured by Chiba Japan)

Sensitizer: 0.4 parts

  (Hodogaya Chemical Co., Ltd. "EAB-F")

Solvent: 23.2 parts

(Propylene glycol monomethyl ether acetate (PGMAC))

(Photosensitive blue coloring composition (RB-1))

After stirring and mixing the mixture of the following composition to be uniform, it was filtered through a 1.0 μm filter to prepare a photosensitive blue colored composition (RB-1).

Colorant dispersion (DB-1): 24.6 parts

  (C.I. Pigment Blue 15: 6 (PB15: 6))

Colorant dispersion (DV-1): 12.9 parts

  (C.I. Pigment Violet 23 (PV23))

Acrylic resin solution 2: 23.0 parts

Photopolymerizable monomer: 2.1 parts

  ("Aronix M402" manufactured by Toagosei)

Photopolymerization initiator: 0.6 parts

  ("Irgacure 907" manufactured by Chiba Japan)

Sensitizer: 0.2 parts

  (Hodogaya Chemical Co., Ltd. "EAB-F")

Solvent: 36.6 parts

(Propylene glycol monomethyl ether acetate (PGMAC))

<Preparation of red coloring composition for organic EL display device>

[Example 201]

(Photosensitive red coloring composition (RR'-101))

The following mixture was stirred and mixed to become uniform, and then filtered through a 1.0 µm filter to prepare a photosensitive coloring composition (RR'-101).

Colorant dispersion (DR-101): 31.2 parts

Colorant dispersion (DR-19): 35.5 parts

Acrylic resin solution 2: 4.3 parts

Photopolymerization monomer: 4.2 parts

  ("Aronix M402" manufactured by Toagosei)

Photopolymerization initiator: 1.2 parts

  ("Irgacure 907" manufactured by Chiba Japan)

Sensitizer: 0.4 parts

  (Hodogaya Chemical Co., Ltd. "EAB-F")

Solvent: 23.2 parts

(Propylene glycol monomethyl ether acetate (PGMAC))

[Examples 202 to 204, Comparative Examples 1 'to 4', 201]

(Photosensitive coloring composition (RR'-21 ~ 24, 102 ~ 104, 201)

Hereinafter, with the exception of changing the coloring composition, acrylic resin solution, photopolymerizable monomer, photopolymerization initiator, sensitizer, and solvent to the types and blending amounts (parts by weight) shown in Table 8, the photosensitive red coloring composition (RR'-1) and In the same manner, photosensitive red coloring compositions (RR'-21 to 24, 102 to 104, 201) were prepared.

In addition, “Aronix M402” manufactured by Toagosei, as a photopolymerizable monomer in Table 8, “Irgacure 907” manufactured by Chiba Japan, was used as a photopolymerization initiator, and “EAB-F” manufactured by Hodogaya Chemical Co., Ltd. was used as a sensitizer.

[Evaluation of photosensitive red coloring composition]

Evaluation of color characteristics and film thickness of the photosensitive red coloring composition obtained in Examples and Comparative Examples was performed by the following method. Table 9 shows the evaluation results.

<Formation of filter segment>

On a glass substrate, a black matrix was pattern-processed, and a coating film of a coloring composition was formed on this substrate using a coloring composition shown in Table 9 with a spin coater. At this time, when the light was irradiated using the organic EL element (EL-1) as the light source, the color characteristics of the red filter segment were respectively coated with a film thickness that can be the values of x and y shown in Table 9. Thereafter, the coating film was irradiated with ultraviolet light of 150 mJ / cm ² through a photomask using an ultra-high pressure mercury lamp. Subsequently, 0.15% by weight of sodium carbonate, 0.05% by weight of sodium hydrogen carbonate, 0.1% by weight of anionic surfactant ("Perirex NBL" manufactured by Kao Corporation) and 99.7% by weight of water were spray-developed with an alkali developer to remove unexposed parts, followed by ion removal. The substrate was washed with exchanged water and the substrate was heated at 230 ° C. for 20 minutes to form a red filter segment shown in Table 9.

<Color characteristics, film thickness evaluation>

The color characteristics (x, y, Y) of the red filter segment when the obtained red filter segment was irradiated with light using organic EL element 1 (EL-1) as a light source was a microscopic spectrophotometer (Olympus Optical Co., Ltd. "OSP" -SP100 ").

The film thickness was measured using a surface shape measuring device DEKTAK150 (manufactured by ULVAC-ES).

The photosensitive coloring composition containing the azo pigment of the present embodiment was able to form within a practical range of a film thickness of 3.0 µm or less, while the filter segment exhibited high brightness Y.

<Production of color filters for organic EL display devices>

[Example 205]

(Color filter (CF-101))

A color filter (CF-1) was produced by obtaining red, green, and blue filter segments in the same manner as in Example 201. However, for the green filter segment, the photosensitive green coloring composition (RG-1) so that the color characteristic when irradiated with light using the organic EL element (EL-1) as the light source is x = 0.200, y = 0.700 The film thickness of the was adjusted. In the blue filter segment, the film thickness of the photosensitive blue coloring composition (RB-1) is such that the color characteristics when irradiating light using the organic EL element (EL-1) as a light source are chromaticities of x = 0.140 and y = 0.080. Was adjusted.

[Comparative Example 202]

(Color filter (CF-201))

Color filter (CF-201) in the same manner as in Example 205 (Color Filter (CF-1)), except that the photosensitive red coloring composition (RR'-201) was used instead of the photosensitive red coloring composition (RR'-101). ).

<Evaluation of color filter>

Color characteristics of the color filter when irradiated with light using organic EL element 1 (EL-1) to the color filters prepared in Examples and Comparative Examples were used by a microscopic spectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). Was measured. Chromaticity point (x, y) in each color filter segment's CIE colorimetric system, NTSC ratio (standard primary tricolor, red (0.67, 0.33), green (0.21, 0.71) as determined by the National Television System Committee (NTSC)) , Blue (0.14, 0.08) and the ratio of the area enclosed by the white light (Y value) is shown in Table 10.

The color filter (CF-101) comprising the red filter segment formed by the red coloring composition containing the azo pigment of this embodiment exhibits a wide color reproducibility of 99% NTSC ratio while maintaining the brightness of a high white display of 18.0. It was confirmed that there was.

Claims (19)

As a pigment composition containing an azo pigment represented by the following general formula (1) and an azo pigment selected from the following general formula (2) and the following general formula (3), the azo pigment represented by the general formula (1) and the general formula ( The pigment composition characterized in that the mass ratio with the azo pigment selected from 2) and general formula (3) is 60.0: 40.0 to 95.0: 5.0.

However, in general formula (1), X ¹ is a hydrogen atom, a chlorine atom, a methoxy group or a methyl group, X ² is a hydrogen atom, X ³ is a hydrogen atom or

, X ⁴ is a trifluoromethyl group, a chlorine atom or a hydrogen atom, X ⁵ is a hydrogen atom, X ⁶ is a methoxy group or a methyl group, X ⁷ and X ⁸ are hydrogen atoms, and X ⁹ is the following formula (d ),

Or a pyridylaminocarbonyl group, and X ¹⁰ is a hydrogen atom.

However, in general formula (2), X ⁶ is a methoxy group or a methyl group, X ⁷ and X ⁸ are hydrogen atoms, and X ⁹ is a group represented by the following formula (d),

Or a pyridylaminocarbonyl group, and X ¹⁰ is a hydrogen atom.

However, in the general formula (3), X ¹ is a chlorine atom, a methyl group or a hydrogen atom, X ² is a hydrogen atom, X ³ is a hydrogen atom or

, X ⁴ is a trifluoromethyl group or a chlorine atom, X ⁵ is a hydrogen atom, X ⁶ is a methoxy group or a methyl group, X ⁷ and X ⁸ are hydrogen atoms, and X ¹⁰ is a hydrogen atom.

However, in formula (d), R ²¹ to R ²⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group, a perfluoroalkyl group, an alkoxyl group, an acetylamino group, a sulfo group and a metal salt thereof, or a group represented by formula (a) to be.

However, in formula (a), n is an integer of 1-10 and R ¹¹ and R ¹² are alkyl groups.
According to claim 1,
Pigment composition in which X ¹ is a chlorine atom, X ⁴ is a trifluoromethyl group, X ² , X ³ , X ⁵ and X ¹⁰ are hydrogen atoms.
According to claim 1,
The pigment composition in which X ⁹ is a group represented by Formula (d).
A coupler component having a mass ratio of a naphthol compound represented by the following general formula (4) and a naphthol compound represented by the following formula (5) is 60.0: 40.0 to 100.0: 0, and an aromatic amine represented by the following general formula (6) and the following general formula The azo pigment represented by the following general formula (1), comprising the step of reacting a diazo compound of an aromatic amine having a mass ratio of 60.0: 40.0 to 100.0: 0 with the aromatic amine represented by (7), and general formula (2) And (3) an azo pigment selected from the method for producing a pigment composition.
However, the case where the mass ratio of the coupler component and the diazo compound of the aromatic amine are both 100.0: 0.

However, in general formula (4), general formula (6) and general formula (7), X ¹ to X ¹⁰ are each independently a hydrogen atom, a halogen atom, an alkyl group, a perfluoroalkyl group, an alkoxyl group, a carbamoyl group, It represents an acetylamino group, a 2-pyridylaminocarbonyl group, or a group represented by the following formulas (a) or (d).

However, in general formula (1), X ¹ is a hydrogen atom, a chlorine atom, a methoxy group or a methyl group, X ² is a hydrogen atom, X ³ is a hydrogen atom or

, X ⁴ is a trifluoromethyl group, a chlorine atom or a hydrogen atom, X ⁵ is a hydrogen atom, X ⁶ is a methoxy group or a methyl group, X ⁷ and X ⁸ are hydrogen atoms, and X ⁹ is the following formula (d ),

Or a pyridylaminocarbonyl group, and X ¹⁰ is a hydrogen atom.

However, in general formula (2), X ⁶ is a methoxy group or a methyl group, X ⁷ and X ⁸ are hydrogen atoms, and X ⁹ is a group represented by the following formula (d),

Or a pyridylaminocarbonyl group, and X ¹⁰ is a hydrogen atom.

However, in the general formula (3), X ¹ is a chlorine atom, a methyl group or a hydrogen atom, X ² is a hydrogen atom, X ³ is a hydrogen atom or

, X ⁴ is a trifluoromethyl group or a chlorine atom, X ⁵ is a hydrogen atom, X ⁶ is a methoxy group or a methyl group, X ⁷ and X ⁸ are hydrogen atoms, and X ¹⁰ is a hydrogen atom.

However, in formula (d), R ²¹ to R ²⁵ are each independently a hydrogen atom, a halogen atom, an alkyl group, a perfluoroalkyl group, an alkoxyl group, an acetylamino group, a sulfo group and a metal salt thereof, or a group represented by formula (a) to be.

However, in formula (a), n is an integer of 1-10 and R ¹¹ and R ¹² are alkyl groups.
The method of claim 4,
The manufacturing method of the pigment composition whose mass ratio of the aromatic amine represented by general formula (6) and the aromatic amine represented by general formula (7) is 100.0: 0.
The method of claim 4,
The manufacturing method of the pigment composition whose mass ratio of the naphthol compound represented by general formula (4) and the naphthol compound represented by general formula (5) is 100.0: 0.
The pigment composition produced by the manufacturing method in any one of Claims 4-6.
A coloring composition comprising a coloring agent, a binder resin, and an organic solvent, wherein the coloring agent contains the pigment composition according to any one of claims 1 to 3.
A coloring composition comprising a coloring agent, a binder resin, and an organic solvent, wherein the coloring agent contains the pigment composition according to claim 7.
The method of claim 8,
A coloring composition characterized by further containing a photopolymerizable monomer.
The method of claim 9,
A coloring composition characterized by further containing a photopolymerizable monomer.
Red pigment for an organic EL display device comprising the pigment composition of claim 1, a binder resin, a photopolymerizable monomer and a photopolymerization initiator, wherein the azo pigment represented by the general formula (1) is an azo pigment represented by the following general formula (1 ') Composition.
Formula (1 ')

However, in the general formula (1 '), X ⁹ represents a carbamoyl group or a group represented by the formula (d). R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, or -OR ⁷ . R ² to R ⁶ each independently represent a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, -OR ⁹ , a carbamoyl group, or an acetylamino group. R ⁷ and R ⁹ each independently represent an alkyl group having 1 to 4 carbon atoms.
The method of claim 12,
A red coloring composition for an organic EL display device, further comprising CI pigment yellow 139 and at least one kind of pigment selected from the quinophthalone compounds represented by the following general formula (2 ').

However, in the general formula (2 '), X1 to X13 are each independently a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkoxyl group that may have a substituent, an aryl group that may have a substituent, -SO ₃ H Group, -COOH group, -SO ₃ H group or -COOH group metal salt, -SO ₃ H group or -COOH group alkylammonium salt, phthalimidemethyl group which may have a substituent, or sulfamoyl group which may have a substituent Indicates. The adjacent groups of X1 to X4 and / or X10 to X13 are united to form an aromatic ring which may have a substituent.
A color filter having a colored film formed by using the red coloring composition for an organic EL display device according to claim 12 or 13, comprising a peak wavelength (λ ₁ ) at which the emission intensity is maximized in a range of at least 430 nm to 485 nm. It has a peak wavelength (λ ₂ ) at which the emission intensity is maximized in the range of wavelengths 560 nm to 620 nm, and the ratio (I2 / I1) of the emission intensity I1 at the wavelength λ ₁ and the emission intensity I2 at the wavelength λ ₂ is 0.4 or more and 0.9 A color filter characterized in that the thickness of the colored film is less than 3.0 µm when the chromaticity coordinates in the XYZ colorimeter of the colored film measured using a white organic EL light source having the following emission spectrum are x≥0.640 and 0.300≤y≤0.360. .
A color filter having a red colored film formed using the red coloring composition for an organic EL display device according to claim 12 or 13, wherein the peak wavelength (λ ₁ ) at which the emission intensity is maximized in a range of at least 430 nm to 485 nm in wavelength. It has a peak wavelength (λ ₂ ) at which the emission intensity is maximized in the range of the over wavelength 560 nm to 620 nm, and the ratio (I2 / I1) of the emission intensity I1 at the wavelength λ ₁ and the emission intensity I2 at the wavelength λ ₂ is 0.4 or more. When a white organic EL light source having a spectral characteristic of 0.9 or less is used, chromaticity coordinates of the red colored film, the green colored film, and the blue colored film in the XYZ color system are (xR, yR), (xG, yG) and (xB), respectively. , yB), the area of the triangle surrounded by these three points is 75% or more with respect to the area surrounded by red (0.67, 0.33), green (0.21, 0.71), and blue (0.14, 0.08). Color filter.
A color filter comprising a filter segment formed of the coloring composition according to claim 8 on a substrate.
A color filter comprising a filter segment formed of the coloring composition according to claim 9 on a substrate.
A color filter comprising a filter segment formed of the coloring composition according to claim 10 on a substrate.
A color filter comprising a filter segment formed of the coloring composition according to claim 11 on a substrate.

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