TWI750402B - Azo pigment, coloring material for color filter, coloring composition for color filter, and color filter - Google Patents

Abstract

An object of the present invention is to provide a coloring composition for a color filter, which is excellent in fastness such as heat resistance and light resistance, has few foreign substances in the coating film, and is good in storage stability, and has high brightness and contrast, and the film thickness changes when the same color is expressed. Thin.

The said subject is solved by the azo pigment which consists of the compound represented by following general formula (1) or general formula (2).

[In the general formula (1), R ₁ represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.

X ₁ to X ₄ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, or a halogen atom]

[In the general formula (2), R ₄ represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.

X ₅ to X ₁₂ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, a hydroxyl group, a cyano group, a nitro group, or a halogen atom. A represents a direct bond or a divalent linking group. The divalent linking group which may have substituent group of alkylene, -O -, - S -, - CO -, - SO 2 -, - COO -, - CONH-, or -SO ₂ NH-]

Description

Azo pigment, colorant for color filter, coloring composition for color filter, and color filter

The present invention relates to a colorant for a color filter, a coloring composition, and a color filter formed using the coloring composition, and the colorant for a color filter is used for manufacturing a color liquid crystal display device and a color solid-state imaging element Color filters used, etc.

The liquid crystal display device is a display device that performs display by controlling the degree of polarization of the light passing through the first polarizing plate and regulating the amount of light passing through the second polarizing plate by having a liquid crystal layer sandwiched between two polarizing plates. In liquid crystal display devices, a type using a twisted nematic (TN; Twisted Nematic) type liquid crystal has become the mainstream. As other typical methods of liquid crystal display devices, there are an in-plane switching (IPS; In Plane Switching) method in which a pair of electrodes is provided on a substrate on one side and an electric field is applied in a direction parallel to the substrate, a method having a negative dielectric Vertical alignment (VA; Vertical Alignment) method in which anisotropic nematic liquid crystals are vertically aligned, and optically compensated bend (OCB; Optically Compensated Bend) in which optical axes of uniaxial retardation films are orthogonal to each other and optically compensated methods, etc., and each method has been put into practical use.

The liquid crystal display device can realize color display by arranging a color filter between two polarizers. In recent years, as color filters are gradually used in televisions, computer monitors, etc., the requirements for high contrast and high brightness of color filters are increasing.

The color filter consists of the following color filters: a color filter in which two or more fine band (stripe)-shaped filter segments of different hues are arranged in parallel or intersecting on the surface of a transparent substrate such as glass. A light filter, or a color filter formed by arranging fine filter segments in a fixed vertical and horizontal arrangement. The filter segments are as fine as several microns to hundreds of microns, and are arranged in a predetermined arrangement according to each hue.

Generally speaking, in a color liquid crystal display device, a transparent electrode is formed on the color filter by vapor deposition or sputtering to drive the liquid crystal, and an alignment film is formed on the transparent electrode for the liquid crystal to be driven. Aligned in a fixed direction. In order to fully obtain the properties of the transparent electrodes and the alignment films, the transparent electrodes and the alignment films must be formed at a high temperature of generally 200°C or higher, preferably 230°C or higher. Therefore, as a method for producing a color filter, a method called a pigment dispersion method, which uses a pigment excellent in light resistance and heat resistance as a colorant, is currently the mainstream.

Brightness and contrast ratio are mentioned as a quality item requested|required for a color filter. If a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal will be confused, and light leakage will occur when light must be blocked (OFF state), or transmitted light will be attenuated when light must be transmitted (ON state). , resulting in a blurry picture. Therefore, in order to realize a high-quality liquid crystal display device, a high contrast ratio is indispensable.

In addition, when a color filter with low brightness is used, the transmittance of light is low, and thus a dark screen is obtained. In order to obtain a bright screen, the number of backlights as light sources must be increased. Therefore, from the viewpoint of suppressing an increase in power consumption, there has been a trend toward higher luminance of color filters. Furthermore, as described above, color liquid crystal devices are gradually being used in televisions, computer monitors, and the like, so that the requirements for high brightness, high contrast, and high reliability of color filters are also increasing.

For the red filter segment, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate, lightfastness and light resistance such as diketopyrrolopyrrole pigments, anthraquinone pigments or perylene pigments are generally used alone or in combination. Pigments with excellent heat resistance are used as colorants.

Among the above pigment species, from the viewpoint of brightness, CI Pigment Red 254, which is a diketopyrrolopyrrole pigment, was used as the main pigment, and from the viewpoint of contrast ratio, CI Pigment Red 177, which was an anthraquinone pigment, was used. as the main pigment. Among them, since the spectral transmittance of C.I. Pigment Red 177 is lower than that of C.I. Pigment Red 254, and the spectral shape is also poor, the addition of C.I. Pigment Red 177 has the disadvantage of causing a decrease in brightness. Therefore, it is desired to develop a C.I. Pigment Red 177 substitute material excellent in brightness.

In recent years, in order to achieve high brightness and high tinting strength, it has been proposed to use an azo pigment represented by C.I. Pigment Red 269 or a disazo pigment described in Patent Document 3 as a main pigment. However, since the affinity of the pigment to the solvent or the acidity of the pigment surface is different from that of CI Pigment Red 254 or CI Pigment Red 177, etc., it also has poor dispersibility, fluidity, storage stability, and further heat resistance and light resistance. The disadvantage is that the performance is also poor, and a practical color filter cannot be obtained. In addition, azo pigments such as C.I. Pigment Red 269 sometimes have a problem of lowering brightness due to color transfer to adjacent other color filter segments, and have high requirements for dye migration.

In Patent Documents 1 to 3, in order to further improve the brightness of the red filter segment, it is proposed to use C.I. Pigment Red 177, C.I. Pigment Red 269, and the disazo pigments described in Patent Document 3 as main pigments. However, the methods of Patent Documents 1 to 3 cannot obtain sufficient brightness, and further improvement is required.

[Prior Art Literature]

[Patent Literature]

Patent Document 1: Japanese Patent Laid-Open No. 2008-304521.

Patent Document 2: Japanese Patent Application Laid-Open No. 2007-533802.

Patent Document 3: Japanese Patent Laid-Open No. 2014-160160.

An object of the present invention is to provide a coloring composition for color filters, which is excellent in fastness such as heat resistance and light resistance, has few foreign matters in the coating film, has good storage stability, has low dye migration, and has high brightness and contrast. The film thickness becomes thinner for the same color.

The inventors of the present invention have repeatedly studied and found that the above-mentioned problems can be solved by using an azo pigment having a specific structure as a colorant for a color filter, thereby completing the present invention.

That is, an embodiment of the present invention relates to an azo pigment composed of a compound represented by the following general formula (1) or general formula (2).

[In the general formula (1), R ₁ represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.

X ₁ to X ₄ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, or a halogen atom]

[In the general formula (2), R ₄ represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.

X ₅ to X ₁₂ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, a hydroxyl group, a cyano group, a nitro group, or a halogen atom. A represents a direct bond or a divalent linking group. The divalent linking group which may have substituent group of alkylene, -O -, - S -, - CO -, - SO 2 -, - COO -, - CONH-, or -SO ₂ NH-]

Moreover, the embodiment of this invention relates to the coloring agent for color filters containing the said azo pigment.

Moreover, the embodiment of this invention is related with the coloring composition for color filters which contains at least a coloring agent and a binder resin, and the said coloring agent is the said coloring agent for color filters.

Moreover, embodiment of this invention is about the said coloring composition for color filters which further contains the resin type dispersing agent which has an acidic substituent.

Moreover, embodiment of this invention is related with the said coloring composition for color filters in which the said resin-type dispersing agent which has an acidic substituent is a resin-type dispersing agent which has an aromatic carboxyl group.

In addition, an embodiment of the present invention relates to the aforementioned coloring composition for a color filter, which further contains a dye derivative, and the dye derivative includes a dye derivative having a basic substituent.

In addition, an embodiment of the present invention relates to the coloring composition for a color filter, wherein the coloring agent further contains a composition selected from the group consisting of CI Pigment Red 254, CI Pigment Red 242, CI Pigment Yellow 138, CI Pigment Yellow 139, CI At least one of the group consisting of Pigment Yellow 150, a yellow pigment represented by the following general formula (3), and a brominated diketopyrrolopyrrole pigment.

[In the general formula (3), Z ₁ to Z ₁₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, -SO ₃ H, -COOH, and monovalent to trivalent metal salts of these acidic groups, alkylammonium salts, phthalimidomethyl which may have substituents, or sulfasulfonates which may have substituents base.

Adjacent groups in Z ₁ to Z ₄ and/or Z ₁₀ to Z ₁₃ may be integrated to form an aromatic ring which may have a substituent]

Moreover, embodiment of this invention is about the said coloring composition for color filters which further contains a photopolymerizable monomer.

In addition, an embodiment of the present invention relates to a color filter including a filter segment on a substrate, and the filter segment is formed of the coloring composition for a color filter.

According to the present invention, the excellent effect is that a coloring composition for a color filter and a color filter can be provided, the coloring composition for a color filter being excellent not only in fastness such as heat resistance and light resistance, but also in a coating film. There are few foreign substances, good storage stability, low dye migration, and high brightness and contrast, and the film thickness becomes thinner when the same color is expressed.

Hereinafter, the present invention will be described in detail. In addition, in this specification, it is expressed as "(meth)acryloyl group", "(meth)acrylic group", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylate group". In the case of “acrylamide”, “acryl and/or methacryl”, “acryl and/or methyl”, “acryl and/or methyl”, respectively, unless otherwise specified acrylic acid, acrylate and/or methacrylate, or acrylamide and/or methacrylamide. In addition, "C.I." mentioned in this specification means a color index (C.I.).

<Azo Pigment>

First, the azo pigment which consists of the compound represented by General formula (1) or General formula (2) of this invention is demonstrated. In addition, in this specification, "the azo pigment composed of the compound represented by the general formula (1) or the general formula (2)" may be abbreviated as "pigment", and "colorant for color filter" may be abbreviated as "pigment". It is abbreviated as "colorant" and will be described.

In the general formula (1), R ₁ represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted aryloxy group. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.

X ₁ to X ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, or a halogen atom.

_{In addition, each of R 1} , R ₂ and R ₃ which are present in plural in the general formula (1) may be the same or different from each other.

In R ₁ , examples of the "halogen atom" include fluorine, bromine, chlorine, and iodine, and among these, chlorine is preferred.

In R ₁ , examples of the "optionally substituted alkyl group" include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, tert-pentyl, 2-ethylhexyl, stearyl, chloromethyl, trichloromethyl, trifluoromethyl, 2-methoxyethyl, 2-chloroethyl, 2-nitroethyl, cyclopentyl, cyclo A hexyl group, a dimethylcyclohexyl group, etc., among these, a methyl group and a trifluoromethyl group are preferable.

In R ₁ , examples of "alkoxy which may have a substituent" include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, n-octoxy, 2-ethyloxy Hexyloxy, trifluoromethoxy, cyclohexyloxy, stearyloxy, 2-(diethylamino)ethoxy, etc. Among them, methoxy, trifluoromethyl are preferred Oxy group, among them, a methoxy group is particularly preferred.

In R ₁ , examples of the "aryloxy group which may have a substituent" include phenoxy, naphthyloxy, 4-methylphenoxy, 3,5-chlorophenoxy, 4-chloro-2- methylphenoxy, 4-tert-butylphenoxy, 4-methoxyphenoxy, 4-diethylaminophenoxy, 4-nitrophenoxy, etc., among them, Phenoxy is preferred.

In R ₂ and R ₃ , examples of the "optionally substituted alkyl group" include methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, tertiary Amyl, 2-ethylhexyl, stearyl, chloromethyl, trichloromethyl, trifluoromethyl, 2-methoxyethyl, 2-hydroxyethyl, 2-chloroethyl, 2-nitro ethyl, cyclopentyl, cyclohexyl, dimethylcyclohexyl, etc., preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, isobutyl, 2- Hydroxyethyl.

In R ₂ and R ₃ , examples of the substituent of the "phenyl group which may have a substituent" include _{a halogen atom in R 1} , an alkyl group which may have a substituent group, an alkoxy group which may have a substituent group, and an alkyl group which may have a substituent group. In addition to these, the aryloxy group having a substituent includes a hydroxyl group, an amino group, -NR ₇ R ₈ , a sulfo group, -SO ₂ NR ₉ R ₁₀ , -COOR ₁₁ , -CONR ₁₂ R ₁₃ , nitro group, cyano group.

The aforementioned R ₇ to R ₁₃ each independently represent a hydrogen atom, an alkyl group which may have a substituent group, and the "alkyl group which may have a substituent group" is preferably an amino group, a monoalkylamine group, or a dialkylamine group substituted alkyl.

X ₁ to X _{4 is,} as "the alkyl group may have a substituent" for R ₁ in "the alkyl group may have a substituent group" meaning the same, preferably methyl, ethyl, trifluoromethyl.

In X ₁ to X ₄ , the "alkoxy group which may have a substituent" has the same meaning as the "alkoxy group which may have a substituent _{" in R 1.}

In the general formula (2), R ₄ represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted aryloxy group. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.

X ₅ to X ₁₂ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, a hydroxyl group, a cyano group, a nitro group, or a halogen atom. A represents a direct bond or a divalent linking group. The divalent linking group which may have substituent group of alkylene, -O -, - S -, - CO -, - SO 2 -, - COO -, - CONH-, or -SO ₂ NH-.

_{In addition, each of R 4} , R ₅ and R ₆ which are present in plural in the general formula (2) may be the same or different from each other.

In R ₄ , "halogen atom", "alkyl group which may have substituent group", "alkoxy group which may have substituent group", and "aryloxy group which may have substituent group" and "halogen atom" in _{R 1} , "the alkyl group which may have a substituent", the "alkoxy group which may have a substituent", and the "aryloxy group which may have a substituent" have the same meaning.

In R ₅ and R ₆ , "alkyl which may have a substituent", "phenyl which may have a substituent" and "alkyl which may have a substituent", "alkyl which may have a substituent" in R ₂ and R ₃ phenyl" has the same meaning.

In X ₅ to X ₁₂ , as "alkyl which may have substituent", "alkoxy which may have substituent", and "alkyl which may have substituent", "alkyl which may have substituent" in R ₁ "Alkoxy" has the same meaning.

In A, examples of the alkylene group which may have a substituent include methylene, ethylidene, n-propylidene, n-butylene, n-hexylidene, n-heptylidene, n-octylidene, and n-dodecylidene. Examples of the substituent include "an alkyl group which may have a substituent" represented by _{R 1 .}

General formula (2) as A, preferred is a group may have a substituent of alkylene, -O -, - S -, - CO -, - SO 2 -, wherein, particularly preferably -SO ₂ -.

<Colorant for Color Filters>

The colorant for color filters of the present invention contains an azo pigment composed of a compound represented by general formula (1) or general formula (2). In the colorant for color filters of the present invention, in order to adjust the chromaticity, etc., a pigment other than the compound represented by the general formula (1) or the general formula (2) may be used together within a range that does not impair the effects of the present invention. or other colorants such as dyes. These pigments and dyes can be used alone or in a mixture of two or more in an arbitrary ratio as needed.

Examples of other colorants include CI Pigment Red 7, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81:1 3. 81: 4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 269, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287 red pigments. As red dyes, dibenzopyran dyes, azo (pyridone-based, barbituric acid-based, etc.) dyes, disazo dyes, anthraquinone dyes, methine dyes, and the like can be mentioned. In addition, it can also be lake pigments obtained by laked these dyes, inorganic salts of acid dyes with acidic groups such as sulfonic acid or carboxylic acid, salt-forming compounds of acid dyes and nitrogen-containing compounds, and acid dyes. Sulfonamide compounds and other forms.

In addition, orange pigments such as CI Pigment Orange 43, 71, or 73 and/or CI Pigment Yellow 1, 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, 221 or represented by the following general formula (3) Yellow paint. In addition, examples of orange dyes and/or yellow dyes include quinoline-based, azo-based (pyridone-based, barbituric-acid-based, metal complex-based, etc.), disazo-based, methine-based, and the like. .

Preferable colorants among the colorants to be used in combination include azo-based, naphthol-azo-based, diketopyrrolopyrrole from the viewpoint of fastness such as heat resistance and light resistance, and chromaticity range. Series, anthraquinone, quinophthalone, and perylene pigments. Specifically, CI Pigment Red 269, 177, 254, 242, CI Pigment Yellow 138, 139, 150, 185, yellow pigments represented by the following general formula (3), and brominated diketopyrrolo Pyrrole pigments.

In particular, from the viewpoint of brightness and tinting strength, CI Pigment Red 254, 242, CI Pigment Yellow 138, 139, 150, a yellow pigment represented by the following general formula (3), and dibromide are more preferable. Ketopyrrolopyrrole pigments.

[In the general formula (3), Z ₁ to Z ₁₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, -SO ₃ H, -COOH, and monovalent to trivalent metal salts of these acidic groups, alkylammonium salts, phthalimidomethyl which may have substituents, or sulfasulfonates which may have substituents base.

Adjacent groups among Z ₁ to Z ₄ and/or Z ₁₀ to Z ₁₃ may be integrated to form an aromatic ring which may have a substituent.

Here, as a halogen atom, fluorine, chlorine, bromine, and iodine are mentioned.

Moreover, as an alkyl group which may have a substituent, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group, Linear or branched alkyl groups such as stearyl and 2-ethylhexyl, and trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-difluoromethyl, etc. Bromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, 2,4-dichlorobenzyl and other substituted alkyl groups.

Moreover, as an alkoxy group which may have a substituent, a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a tert-butoxy group, a neopentyl group can be mentioned. oxy, 2,3-dimethyl-3-pentyloxy, n-hexyloxy, n-octyloxy, stearyloxy, 2-ethylhexyloxy and other linear or branched alkoxy groups, in addition, Also exemplified: trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2-di-trifluoro Substituted alkoxy groups such as methylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, and benzyloxy.

Further, examples of the aryl group which may have a substituent include aryl groups such as phenyl, naphthyl, and anthracenyl, and also include p-methylphenyl, p-bromophenyl, p-nitrophenyl, p- Methoxyphenyl, 2,4-dichlorophenyl, pentafluorophenyl, 2-aminophenyl, 2-methyl-4-chlorophenyl, 4-hydroxy-1-naphthyl, 6-methyl Aryl groups with substituents such as base-2-naphthyl, 4,5,8-trichloro-2-naphthyl, anthraquinone, 2-aminoanthraquinone, etc.

In addition, examples of the acidic group include -SO ₃ H and -COOH, and examples of the monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, Aluminum salts, etc. Further, examples of the alkylammonium salt of the acidic group include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, and stearylamine, palmityltrimethylammonium, and dilauryldimethylammonium. ammonium, distearyl dimethyl ammonium salt and other quaternary alkyl ammonium salts.

Among the optionally substituted phthalimidomethyl group (C ₆ H ₄ (CO) ₂ N-CH ₂ -) and the optionally substituted sulfamoyl group (H ₂ NSO ₂ -) The "substituent" includes the above-mentioned halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, and the like.

_{Adjacent groups in Z 1} to Z ₄ and/or Z ₁₀ to Z ₁₃ of the general formula (3) may be integrated to form an aromatic ring which may have a substituent. The aromatic ring referred to here includes a hydrocarbon aromatic ring and a heteroaromatic ring, and the hydrocarbon aromatic ring includes a benzene ring, a naphthalene ring, an anthracene ring, a phenanthrene ring, and the like, and the heteroaromatic ring includes a pyridine ring , pyrazine ring, pyrrole ring, quinoline ring, quinoxaline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, oxazole ring, thiazole ring, imidazole ring, pyrazole ring, indole ring , carbazole ring, etc.

Specific examples of the yellow pigment represented by the general formula (3) used in the colorant for color filters of the present invention include the following quinophthalone compounds (a) to quinophthalone compounds (r ) etc., but the present invention is not limited to these. In addition, the quinophthalone compound used in the present invention can be produced, for example, by the method described in Japanese Patent Publication No. 2930774, but the present invention is not limited to these.

Quinophthalone compound (q) Quinophthalone compound (r)

As the dye that can be used together, it is preferably a dye that exhibits red or purple, and has any form of oil-soluble dye, acid dye, direct dye, and basic dye.

Among these, it is preferable to use a dibenzopyran-type oil-soluble dye, a dibenzopyran-type basic dye, and a dibenzopyran-type acid dye because the hue is excellent. In addition, it can also be lake pigments obtained by laked these dyes, inorganic salts of acid dyes with acidic groups such as sulfonic acid or carboxylic acid, salt-forming compounds of acid dyes and nitrogen-containing compounds, and acid dyes. Sulfonamide compounds and other forms.

Examples of dibenzopyran-based oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, CI Solvent Red 45, CI Solvent Red 46, CI Solvent Red 47, CI Solvent Red 48, CI Solvent Red 49, CI Solvent Red 72, CI Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet 10, etc. Among them, CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 49, CI Solvent Red 109, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Red 237, CI Solvent Red 246 and CI Solvent Red Purple 2.

Examples of the dibenzopyran-based basic dye include C.I. Basic Red 1 (Rose Bengal 6GCP), 8 (Rose Bengal G), C.I. Basic Violet 10 (Rose Bengal B), and the like. Among them, C.I. Basic Red 1 and C.I. Basic Violet 10 are preferably used in terms of excellent color rendering properties.

As the dibenzopyran-based acid dye, it is preferable to use CI Acid Red 51 (Chrysanthemum Red (Edible Red No. 3)), CI Acid Red 52 (Acid Rose Bengal), CI Acid Red 87 (Eosin G (Edible Red No. 3) Red No. 103)), CI Acid Red 92 (Acid Oleander Red PB (Edible Red No. 104)), CI Acid Red 289, CI Acid Red 388, Bengal Rose Red B (Edible Red No. 5), Acid Rose Red G, CI Acid Violet 9.

Among them, in terms of heat resistance and light resistance, it is more preferable to use CI Acid Red 87, CI Acid Red 92, CI Acid Red 388, which are dibenzopyran-based acid dyes, or those that are Rose Bengal acid dyes. CI Acid Red 52 (Acid Rose Bengal), CI Acid Red 289, Acid Rose Bengal G, CI Acid Violet 9.

Among these dyes, C.I. Acid Red 52, which is a rose bengal-based acid dye, is most preferably used in terms of excellent color development, heat resistance, and light resistance.

When used together with the above-mentioned red pigment, yellow pigment, orange pigment, and dye, the content of the compound represented by the above general formula (1) or general formula (2) is 10% by mass in the total 100% by mass of the colorant to 90% by mass, preferably 20% to 80% by mass. When content of the compound represented by the said general formula (1) or general formula (2) is 10 mass % or less, the effect which is excellent in brightness and tinting strength cannot be fully exhibited.

<Average Primary Particle Size of Pigment>

The average primary particle diameter of the pigment was measured (calculated) by the following method.

Propylene glycol monomethyl ether acetate was added to the pigment powder, and a small amount of Disperbyk-161 was added as a resin-type dispersant, and dispersed for 1 minute with an ultrasonic cleaner to prepare a sample for measurement. For this sample, three pictures (three fields of view) were taken with a transmission electron microscope (“JEM-1200EX” manufactured by JEOL Ltd.) in which primary particles of 100 or more pigments could be confirmed. Sequentially determine the size of 100 primary particles. Specifically, the short-axis diameter and long-axis diameter of the primary particles of each pigment are measured in nanometer units, and the average of the short-axis diameter and long-axis diameter is regarded as the primary particle size of the pigment, and the scale is every 5 nm. For a distribution of a total of 300 particles, the median value of each 5 nm scale (for example, 8 nm in the case of 6 nm or more and 10 nm or less) is approximated as the particle size of these particles, and calculated based on each particle size and its number, thereby The number-average particle diameter was calculated.

<Miniaturization of Colorants>

The pigment used in the present invention can be used by being refined. It is also preferable to use a pigment containing the compound represented by the above-mentioned general formula (1) or general formula (2) for making it finer. The miniaturization method is not particularly limited, and for example, any one of wet milling, dry milling, and dissolution and precipitation can be used, and as exemplified in the present invention, a kneader method, which is one type of wet milling, can be performed. The salt milling (salt milling) treatment.

The primary particle diameter of the micronized pigment is preferably 20 nm or more in terms of good dispersion in the colorant carrier. In addition, in terms of forming a filter segment with a high contrast ratio, it is preferably 100 nm or less. A particularly preferred range is the range of 25 nm to 85 nm.

The so-called salt mill treatment refers to the following treatment, that is, the mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent, using a kneader, ternary mixer, two-roll mill, three-roll mill, ball mill, A kneader such as a grinder or a sand mill is mechanically kneaded while heating, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by the high hardness of the inorganic salt at the time of salt milling. By optimizing the conditions when the pigment is subjected to salt milling, it is possible to obtain a pigment with a very fine primary particle size, a narrow distribution range, and a steep particle size distribution.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used, and sodium chloride (table salt) is preferably used in terms of price. In terms of both processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in 50 to 2,000 parts by mass, preferably 300 to 1,000 parts by mass relative to 100 parts by mass of the colorant.

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 is a solvent that dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, since the temperature rises at the time of salt milling and the solvent is easily evaporated, a high-boiling solvent having a boiling point of 120° C. or higher is preferred from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isoamyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol Ethylene 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 monoethyl ether, liquid polypropylene glycol, etc. The water-soluble organic solvent is preferably used in 5 parts by mass to 1000 parts by mass, preferably 50 parts by mass to 500 parts by mass, with respect to 100 parts by mass of the colorant.

When salt-milling the pigment, resin can also be added as needed. 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 at room temperature and insoluble in water, and is further preferably partially soluble in the above-mentioned organic solvent. The usage-amount of resin is preferably in the range of 5 parts by mass to 200 parts by mass with respect to 100 parts by mass of the colorant.

In addition, when salt-milling the pigment, a pigment derivative described later may be added as necessary. The structure of the pigment derivative to be used is not particularly limited, and examples include organic pigments, anthraquinone, acridone, or triazine into which basic substituents, acidic substituents, or phthalates which may have substituents are introduced. The compound of imidomethyl group. These can be used individually or in mixture of 2 or more types.

The usage-amount of these pigment derivatives is preferably 2 to 30 parts by mass, and most preferably 5 to 20 parts by mass, relative to 100 parts by mass of the colorant.

<Coloring composition for color filters>

The coloring composition for color filters of the present invention is composed of a binder resin in addition to the coloring agent described above.

<binder resin>

The binder resin is a resin that disperses, dyes, or penetrates a colorant, and examples thereof include thermoplastic resins and the like. Moreover, when using in the form of an alkali-developing-type coloring resist material, it is preferable to use the alkali-soluble vinyl-type resin which copolymerized the ethylenically unsaturated monomer containing an acidic group. Moreover, in order to further improve the photosensitivity, the active energy ray curable resin which has an ethylenically unsaturated double bond can also be used.

In particular, by using an active energy ray-curable resin having an ethylenically unsaturated double bond in the side chain for an alkali-developing coloring resist material, and when forming a coating film by exposure to active energy rays, the resin is The colorant is fixed by three-dimensional crosslinking, the heat resistance becomes favorable, and the discoloration (deterioration of the spectroscopic characteristics) of the colorant due to heat can be suppressed. In addition, it also has the effect of suppressing aggregation and precipitation of colorant components in the developing step.

The binder resin is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 nm to 700 nm in the visible light region.

The weight-average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, more preferably in the range of 10,000 to 80,000, in order to make the colorant better disperse. In addition, the number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw/Mn is preferably 10 or less.

When a binder resin is used in a photosensitive coloring composition for color filters, a carboxyl group that functions as a colorant adsorption group and an alkali-soluble group during development, and an affinity group for a colorant carrier and a solvent The balance of the functioning aliphatic group and aromatic group is important for the dispersibility, permeability, developability, and durability of the colorant, and it is preferable to use a resin with an acid value of 20 mgKOH/g to 300 mgKOH/g. If the acid value is less than 20 mgKOH/g, the solubility with respect to the developing solution is poor, and it is difficult to form a fine pattern. If it exceeds 300 mgKOH/g, the fine pattern cannot remain.

The binder resin is preferably used in an amount of 20 parts by mass or more with respect to 100 parts by mass of the total mass of the colorant in terms of good film-forming properties and various resistances. In terms of color characteristics, it is preferably used in an amount of 1,000 parts by mass or less.

As the thermoplastic resin used for the binder resin, for example, acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride- Vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber Resin, cellulose, polyethylene (HDPE (High Density Polyethylene, High Density Polyethylene), LDPE (Low Density Polyethylene, Low Density Polyethylene)), polybutadiene, and polyimide resin, etc. Among them, an acrylic resin is preferably used.

As an ethylenic alkali-soluble resin which copolymerized an acidic-group containing ethylenically unsaturated monomer, the resin which has acidic groups, such as a carboxyl group and a sulfanyl group, is mentioned, for example.

Specific examples of the alkali-soluble resin include acrylic resins having acidic groups, α-olefin/maleic acid (anhydride) copolymers, styrene/styrene sulfonic acid copolymers, ethylene/(methyl) Acrylic copolymer, or isobutylene/maleic acid (anhydride) copolymer, etc. Among them, at least one resin selected from an acrylic resin having an acidic group and a styrene/styrene sulfonic acid copolymer, especially an acrylic resin having an acidic group, can be preferably used because of its high heat resistance and transparency.

As an active energy ray-curable resin which has an ethylenically unsaturated double bond, the resin which introduce|transduced the unsaturated ethylenic double bond by the method of (i) or (ii) shown below is mentioned, for example.

[Method (i)]

As the method (i), for example, there is a method in which a copolymer is obtained by copolymerizing an unsaturated ethylenic monomer having an epoxy group with one or more other monomers, and the side of the obtained copolymer is The chain epoxy group undergoes an addition reaction with the carboxyl group of the unsaturated monobasic acid having an unsaturated ethylenic double bond, and the generated hydroxyl group is reacted with the polybasic acid anhydride to introduce the unsaturated ethylenic double bond and the carboxyl group.

Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, and 2-glycidyloxyethyl (meth)acrylate. , 3,4 epoxybutyl (meth)acrylate, and 3,4 epoxycyclohexyl (meth)acrylate, these may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid of the next step, glycidyl (meth)acrylate is preferred.

Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, ortho-, meta-, para-vinylbenzoic acid, α-haloalkyl group of (meth)acrylic acid, alkoxy group, halogen group, and nitro group. , monocarboxylic acids such as cyano substituents, etc., and these may be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like, which may be used alone or in combination of two above. The number of carboxyl groups may be increased, and if necessary, tricarboxylic anhydrides such as trimellitic anhydride or tetracarboxylic dianhydrides such as pyromellitic dianhydride may be used, and the remaining anhydride groups may be hydrolyzed. Moreover, when tetrahydrophthalic anhydride or maleic anhydride which has an unsaturated ethylenic double bond is used as a polybasic acid anhydride, an unsaturated ethylenic double bond can be increased further.

As a method similar to the method (i), for example, there is a method in which a copolymer is obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers, and the obtained copolymer is A part of the carboxyl group in the side chain undergoes an addition reaction with an unsaturated ethylenic monomer having an epoxy group, thereby introducing an unsaturated ethylenic double bond and a carboxyl group.

[Method (ii)]

As the method (ii), there is a method of obtaining a copolymer by copolymerizing an unsaturated ethylenic monomer having a hydroxyl group with another monomer having an unsaturated monobasic acid having a carboxyl group or other monomers, thereby obtaining the obtained copolymer. The side chain hydroxyl group of the copolymer reacts with the isocyanate group of the unsaturated ethylenic monomer having an isocyanate group.

Examples of the unsaturated ethylenic monomer having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3-(meth)acrylate, or 2- or 3-hydroxypropyl (meth)acrylate. Hydroxyalkyl (meth)acrylates such as 4-hydroxybutyl ester, glycidyl (meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate, which can be used alone or in combination of 2 more than one species. In addition, polyether mono(meth)acrylates obtained by addition-polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to the above-mentioned hydroxyalkyl (meth)acrylates can also be used, or (Poly)ester mono(meth)acrylate obtained by adding (poly)γ-valerolactone, (poly)ε-caprolactone, and/or (poly) 12-hydroxystearic acid. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl (meth)acrylate or glycidyl (meth)acrylate is preferred.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis[(meth)acryloyloxy]ethyl isocyanate. Although ester etc. are not limited to these, You may use 2 or more types together.

<Organic solvent>

The coloring composition of the present invention is based on the purpose of easily dispersing and permeating the colorant in the colorant carrier, and coating it on a substrate such as a glass substrate with a dry film thickness of 0.2 μm to 5 μm to form a filter segment. , may contain organic solvents. The organic solvent is selected in consideration of the solubility of each component of the coloring composition, and further the safety, in addition to the favorable coatability of the coloring composition.

Examples of the organic solvent include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, and 1,3-butanediol diethyl acid ester, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3 ,5-trimethylcyclohexanone, 3-ethoxyethyl propionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, acetic acid 3-methoxy-3-methylbutyl ester, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butanol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chloro Toluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, 2-butylbenzene, 3-butylbenzene, γ-butyrolactone, isobutanol, isophorone, Ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether 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, diisobutyl ketone Ethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetic acid Esters, 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, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol mono Diethyl 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, methyl cyclohexane Alcohol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, etc. These solvents can be used alone or by mixing two or more of them in an arbitrary ratio as needed.

The solvent can be used in an amount of 100 parts by mass to 10,000 parts by mass, preferably 500 parts by mass to 5,000 parts by mass with respect to 100 parts by mass of the colorant in the coloring composition.

<Photopolymerizable monomer>

The photopolymerizable monomers that can be added to the coloring composition of the present invention include monomers or oligomers that are cured by ultraviolet rays, heat, and the like to form transparent resins.

Examples of monomers and oligomers that form transparent resins by curing with ultraviolet rays or heat include methyl (meth)acrylate, ethyl (meth)acrylate, and 2-hydroxyethyl (meth)acrylate. , 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanedi Alcohol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate Acrylates, 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, tricyclodecyl(meth)acrylate, ester acrylate, methylolated Various acrylates and methacrylates such as (meth)acrylates of melamine, epoxy (meth)acrylates, urethane acrylates, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl Vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, etc., but not necessarily limited to these. These photopolymerizable compounds can be used individually by 1 type, or can mix and use 2 or more types by arbitrary ratios as needed.

The content of the photopolymerizable monomer is preferably 5 parts by mass to 500 parts by mass with respect to 100 parts by mass of the colorant, and more preferably 10 parts by mass to 400 parts by mass from the viewpoint of photocurability and developability.

<Photopolymerization initiator>

A photopolymerization initiator can be added to the coloring composition of the present invention to prepare it in the form of a solvent-developing or alkali-developing photosensitive coloring composition, so that the composition can be cured by irradiation with ultraviolet rays by photolithography. Form filter segments.

As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-tert-butyldichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl) can be used )-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropane -1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone , or 2-benzyl-2-dimethylamino-1-(4-morpholinyl phenyl)-butane-1-one and other acetophenone compounds; benzoin, benzoin methyl ether, benzoin ether, benzoin Benzoin-based compounds such as isopropyl ether, or benzophenone dimethyl ketal; benzophenone, benzylbenzoic acid, methyl benzylbenzoate, 4-phenylbenzophenone, Hydroxybenzophenone, acrylated benzophenone, 4-benzyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(tert-butylperoxide) Carbonyl) benzophenone and other benzophenone compounds; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Ketones, or thioxanthone-based compounds such as 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine oxazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine , 2-sunflower base-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphthalene-1-yl )-4,6-bis(trichloromethyl)s-triazine, 2-(4-methoxy-naphthalen-1-yl)-4,6-bis(trichloromethyl)s-triazine, 2, Triazine compounds such as 4-trichloromethyl-(sunyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; 1 , 2-octanedione, 1-[4-(phenylthio)-2-(O-benzyl oxime)], or O-(acetyl)-N-(1-phenyl-2- Oxime ester compounds such as pendant oxy-2-(4'-methoxy-naphthyl) ethylene) hydroxylamine; bis(2,4,6-trimethylbenzyl)phenylphosphine oxide, Or phosphine compounds such as 2,4,6-trimethylbenzyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole series compounds; imidazole series compounds; or titanocene series compounds, etc. These photopolymerization initiators can be used individually by 1 type, or can mix and use 2 or more types by arbitrary ratios as needed.

The content of the photopolymerization initiator is preferably 1 part by mass to 500 parts by mass relative to 100 parts by mass of the colorant, and more preferably 5 parts by mass to 400 parts by mass from the viewpoint of photocurability and developability.

<Sensitizer>

Furthermore, a sensitizer may be contained in the coloring composition for color filters of this invention.

Examples of sensitizers include unsaturated ketones represented by chalcone derivatives, dibenzylideneacetone, etc., 1,2-diketone derivatives represented by benzil, camphorquinone, etc., and benzoin. Derivatives, stilbene derivatives, naphthoquinone derivatives, anthraquinone derivatives, dibenzopyran (xanthene) derivatives, thioxanthene (thioxanthene) derivatives, xanthone (xanthone) derivatives, thioxanthene ( thioxanthone) derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxazine derivatives, acridine derivatives, azine derivatives , Thiazine Derivatives, Oxazine Derivatives, Indoline Derivatives, Azulene Derivatives, Azulium Derivatives, Squarium Derivatives, Porphyrin Derivatives, Tetraphenyl Porphyrin Derivatives, Triarylmethane Derivatives , Tetrabenzoporphyrin Derivatives, Tetrapyrazine Porphyrazine Derivatives, Phthalocyanine Derivatives, Tetraaza Porphyrazine Derivatives, Tetraquinoxaline Porphyrazine Derivatives, Naphtholcyanine Derivatives, Subphthalocyanine Derivatives Derivatives, pyrylium derivatives, thiopyranium derivatives, tetraphyllin derivatives, rotaxene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives , metal arene complexes, organo-ruthenium complexes, Michler's ketone derivatives, etc. These sensitizers can be used individually by 1 type, or can mix and use 2 or more types by arbitrary ratios as needed.

Further, specific examples include: "Handbook of Pigments" edited by Nobu Ogawara et al. (1986, Kodansha), "Chemistry of Functional Pigments" edited by Nobu Ogawara et al. The sensitizers described in "Special Functional Materials" (1986, CMC) edited by Ren are not limited to these. In addition, a sensitizer that exhibits absorption to light in the ultraviolet to near-infrared region may also be contained.

Among the above-mentioned sensitizers, particularly preferred sensitizers include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. Furthermore, specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropyl can be used Thioxanthone, 1-Chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)diphenyl ketone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzyl-N-ethylcarbazole, 3,6-dibenzyl Acyl-N-ethylcarbazole, etc.

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

<Multifunctional Thiol>

The coloring composition for color filters of this invention may contain a polyfunctional thiol. The polyfunctional thiol is a compound having two or more thiol (SH) groups. When used together with the above-mentioned photopolymerization initiator, the polyfunctional thiol acts as a chain transfer agent in the radical polymerization process after light irradiation, and generates sulfur radicals that are not easily hindered by the polymerization caused by oxygen. (thiyl radical), the obtained coloring composition for color filters has high sensitivity. Particularly preferred is a polyfunctional aliphatic thiol in which an SH group is bonded to an aliphatic group such as a methylene group and an ethylidene group.

Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithioglycolate, Ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolethane Tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptopropionate), pentaerythritol tetrathioglycolate, pentaerythritol tetrakis Thiopropionate, Pentaerythritol tetrakis(3-mercaptopropionate), Dipentaerythritol hexa(3-mercaptopropionate), Tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4 -Dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. These polyfunctional thiols can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

The content of the polyfunctional thiol is preferably 0.05 parts by mass to 100 parts by mass, more preferably 1.0 parts by mass to 50.0 parts by mass with respect to 100 parts by mass of the colorant.

By using 0.05 mass part or more of polyfunctional thiol, more favorable development resistance can be obtained. In the case of using a monofunctional thiol having one thiol (SH) group, such an improvement in development resistance cannot be obtained.

<Leveler>

In the coloring composition of the present invention, it is preferable to add a leveling agent so that the leveling property of the composition on the transparent substrate is good. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure on the main chain is preferable. As a specific example of the dimethylsiloxane which has a polyether structure in a main chain, FZ-2122 by Dow Corning Toray Co., Ltd., BYK-333 by BYK-Chemie Co., Ltd., etc. are mentioned. Specific examples of the dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can also be used in combination. The content of the leveling agent is usually 0.003 to 1.0 parts by mass relative to 100 parts by mass of the total mass of the coloring composition.

As a particularly preferred leveling agent, it is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, and has the following characteristics: although it has a hydrophilic group, it has low solubility in water, and it is added to the coloring composition. In this case, the surface tension reducing ability of the leveling agent is low. The leveling agent is further useful because the leveling agent has good wettability to the glass plate despite the low surface tension reducing ability, and can be preferably used in an amount added that does not cause coating film defects due to foaming. A leveling agent that sufficiently suppresses electrification. As a leveling agent having such preferable properties, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. The polyalkylene oxide unit includes a polyethylene oxide unit and a polypropylene oxide unit, and the dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

In addition, the bonding form of the polyalkylene oxide unit and the dimethylpolysiloxane may be a side chain type in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethylpolysiloxane, or a dimethylpolysiloxane bond. Either of the terminal-modified type at the end of the base polysiloxane, and the linear block copolymer type in which dimethylpolysiloxane is alternately and repeatedly bonded. Dimethyl polysiloxane having a polyalkylene oxide unit is marketed by Dow Corning Toray Co., Ltd., for example: FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191 , FZ-2203, FZ-2207, but not limited to these.

In the leveling agent, anionic, cationic, nonionic, or amphoteric surfactants can also be supplementarily added. Two or more types of surfactants may be mixed and used. Examples of anionic surfactants to be supplementarily added to the leveling agent include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, alkyl Sodium Naphthalene Sulfonate, Sodium Alkyl Diphenyl Ether Disulfonate, Monoethanolamine Lauryl Sulfate, Triethanolamine Lauryl Sulfate, Ammonium Lauryl Sulfate, Monoethanolamine Stearate, Sodium Stearate, Sodium Lauryl Sulfate, Styrene - Monoethanolamine of acrylic copolymer, polyoxyethylene alkyl ether phosphate, etc.

As a cationic surfactant to be added to the leveling agent auxiliary, an alkyl quaternary ammonium salt or its ethylene oxide adduct can be mentioned. Examples of nonionic surfactants auxiliaryly added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, Polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc. In addition, examples of the amphoteric surfactant to be supplementarily added to the leveling agent include alkylbetaines such as alkyldimethylaminoacetate betaine, and amphoteric surfactants such as alkylimidazoline.

<Ultraviolet absorber, polymerization inhibitor>

The coloring composition for color filters of the present invention may contain an ultraviolet absorber or a polymerization inhibitor. By containing an ultraviolet absorber or a polymerization inhibitor, the shape and imageability of the pattern can be controlled.

As the ultraviolet absorber, for example, 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4 ,6-bis(2,4-dimethylphenyl)-1,3,5-triazine, 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4 ,6-bis(4-phenylphenyl)-1,3,5-triazine and other hydroxyphenyltriazine series, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2- (2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(3-tert-butyl-5-methyl-2- Benzotriazoles such as hydroxyphenyl)-5-chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2,2',4 ,4'-tetrahydroxybenzophenone and other benzophenone series, salicylic acid ester such as phenyl salicylate and p-tert-butylphenyl salicylate, 2-cyano-3,3'- Cyanoacrylates such as ethyl diphenylacrylate, 2,2,6,6-tetramethylpiperidine-1-oxyl radical (triacetone-amine-N-oxyl radical), sebacic acid bis( 2,2,6,6-Tetramethyl-4-piperidinyl)ester, poly[[6-[(1,1,3,3-tetrabutyl)amino]-1,3,5-tri Hindered amines such as oxazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino] and the like. These ultraviolet absorbers can be used individually by 1 type, or can mix and use 2 or more types by arbitrary ratios as needed.

Examples of the polymerization inhibitor include methyl hydroquinone, tert-butyl hydroquinone, 2,5-di-tert-butyl hydroquinone, 4-benzoquinone, and 4-methoxyphenol , 4-methoxy-1-naphthol, tertiary butyl catechol and other hydroquinone derivatives and phenol compounds, phenothiazine, bis-(1-dimethylbenzyl) phenothiazine, Amine compounds such as 3,7-dioctylphenothiazine, copper dibutyl dithiocarbamate, copper diethyl dithiocarbamate, manganese diethyl dithiocarbamate, diphenyl Copper and manganese salt compounds such as manganese dithiocarbamate, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, N-nitrosophenylhydroxylamine and other nitroso compounds and their ammonium salts or aluminum salts, etc. These polymerization inhibitors can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

The ultraviolet absorber and the polymerization inhibitor can be used in an amount of 0.01 to 20 parts by mass, preferably 0.05 to 10 parts by mass, relative to 100 parts by mass of the colorant in the coloring composition.

By using 0.01 mass part or more of an ultraviolet absorber or a polymerization inhibitor, a better image formation degree can be obtained.

<Antioxidant>

The coloring composition for color filters of the present invention may contain an antioxidant to improve the transmittance of the coating film. Antioxidant prevents the photopolymerization initiator contained in the coloring composition for color filters from being oxidized and yellowed due to the thermal step during thermal curing or ITO (Indium Tin Oxide) annealing, thereby improving the coating film. transmittance. Therefore, by containing an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high transmittance of the coating film can be obtained.

Preferable antioxidants include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, thioether-based antioxidants, and the like. In addition, a hindered phenol-based antioxidant, a hindered amine-based antioxidant, or a phosphorus-based antioxidant is more preferred. These antioxidants can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

Examples of hindered phenol-based antioxidants include 2,4-bis[(laurylthio)methyl]o-cresol, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl) base), 1,3,5-tris(4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl), and 2,4-bis-(n-octylthio)-6-( 4-Hydroxy-3,5-di-tert-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid esters, etc.

Examples of hindered amine-based antioxidants include bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, bis(N-methyl-2,2,6,6 sebacate) -Tetramethyl-4-piperidinyl) ester, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-1,6-hexamethylenediamine, 2-Methyl-2-(2,2,6,6-tetramethyl-4-piperidinyl)amino-N-(2,2,6,6-tetramethyl-4-piperidinyl) Propionamide, 1,2,3,4-butanetetracarboxylic acid tetrakis(2,2,6,6-tetramethyl-4-piperidinyl) ester, poly[{6-(1,1,3 ,3-Tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6-tetramethyl-4-piperidinyl)idene Amino}hexamethyl{(2,2,6,6-tetramethyl-4-piperidinyl)imino}], poly[(6-morpholino-1,3,5-triazine- 2,4-diyl){(2,2,6,6-tetramethyl-4-piperidinyl)imino}hexamethylene{(2,2,6,6-tetramethyl-4 -Piperidinyl)imino}], the polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, N, N'-4,7-Tetra[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidinyl)amino}-1,3 , 5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, etc.

Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2] Dioxaphosphet-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetratert-butyldibenzo[d,f][1 ,3,2]dioxaphosphacyclohepten-2-yl)oxy]ethyl]amine, ethyl phosphite bis(2,4-ditert-butyl-6-methylphenyl)ester .

Examples of thioether-based antioxidants include 2,2-thio-dieneethylbis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 2,4 -Bis[(octylthio)methyl]o-cresol, 2,4-bis[(laurylthio)methyl]o-cresol, etc.

The content of the antioxidant is preferably used in an amount of 0.1 parts by mass to 5 parts by mass in a total of 100 parts by mass of the solid content of the coloring composition for a color filter. When the antioxidant is less than 0.1 parts by mass, the effect of improving the transmittance is small, and when it is more than 5 parts by mass, the hardness is greatly reduced, and the sensitivity of the coloring composition for a color filter is greatly reduced.

<Other ingredients>

The coloring composition for a color filter of the present invention may contain an adhesion enhancer such as a silane coupling agent to improve adhesion to a transparent substrate, or an amine compound having an action of reducing dissolved oxygen.

Examples of the silane coupling agent include vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, vinylsilanes such as vinyltrimethoxysilane, and γ-methacryloyloxysilane. (Meth)acrylic silanes such as propylpropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethyl Oxysilane, β-(3,4-Epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-Epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxy Epoxysilanes such as propyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β( Aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxy Silane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane and other aminosilanes , γ-mercaptopropyl trimethoxysilane, γ-mercaptopropyl triethoxysilane and other thiosilanes.

The silane coupling agent can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, with respect to 100 parts by mass of the colorant in the coloring composition.

Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylaminobenzoate. Isoamyl aminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, etc.

<The manufacturing method of the coloring composition for color filters>

In the coloring composition for color filters of the present invention, a colorant can be mixed with a colorant carrier such as a resin and/or a solvent, and a kneader, two-roll mill, three-roll mill, ball mill, Various dispersion means, such as a horizontal sand mill, a vertical sand mill, a ring bead mill, or an attritor, are used to finely disperse and manufacture (colorant dispersion). At this time, two or more colorants and the like may be dispersed in the colorant carrier at the same time, or the colorants dispersed in the colorant carrier may be mixed. The epoxy compound can be added at the stage of preparing the colorant dispersion, but the same effect can also be obtained by adding it later to the prepared colorant dispersion. When the solubility of colorants such as dyes is high, specifically, if the solubility in the solvent to be used is high, it is not necessary to disperse to the above-mentioned fineness in order to dissolve by stirring, and in a state where no foreign matter can be confirmed. state to manufacture.

In addition, when the photosensitive coloring composition for color filters is used as a resist material, it can be prepared as a solvent-developing-type or alkali-developing-type coloring composition. The solvent-developing-type or alkali-developing-type coloring composition can be prepared by mixing the aforementioned colorant dispersion, a photopolymerizable monomer and/or a photopolymerization initiator, and optionally a solvent, other pigment dispersants, additives, and the like. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added subsequently to the prepared coloring composition.

<Dispersion Auxiliary>

When dispersing a colorant in a colorant carrier, it is preferable to contain not only a resin-type dispersant but also a dispersing aid such as a pigment derivative and a surfactant. The dispersing assistant has a great effect of preventing the re-agglomeration of the dispersed colorant, so the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersing assistant has good brightness and storage stability.

<Resin type dispersant>

It is preferable that the coloring composition for color filters of this invention further contains the resin type dispersing agent which has an acidic substituent.

Resin-type dispersants have a colorant-affinity site (having the property of being adsorbed to the colorant) and a site that is compatible with the colorant carrier, and the colorant is adsorbed to the colorant to stabilize the dispersion of the colorant in the colorant carrier. effect. As the resin type dispersant, specifically, polycarboxylate such as polyurethane and polyacrylate, unsaturated polyamide, polycarboxylic acid, polycarboxylic acid (partial) amine salt, polycarboxylic acid can be used Ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyamidoamine phosphates, hydroxyl-containing polycarboxylates, or their modifications, by poly(lower alkenimine) Oil-based dispersants such as amides or their salts formed by the reaction with polyesters having free carboxyl groups, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene - Maleic acid copolymer, polyvinyl alcohol, polyvinyl pyrrolidone and other water-soluble resins or water-soluble polymer compounds, polyester series, modified polyacrylate series, ethylene oxide/propylene oxide compound A compound, a phosphoric acid ester, etc., these can be used individually or in mixture of 2 or more types, but are not necessarily limited to these.

Commercially available resin-based dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165 manufactured by BYK-Chemie Japan , 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, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, manufactured by Lubrizol, Japan, Made by BASF company ,48,452,4008,4009,4010,4015,4020,4047,4050,4055,4060,4080,4400,4401,4402,4403,4406,4408,4300,4310,4320,4330,4340,450,451 , 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., manufactured by Ajinomoto Fine-Techno Ajisper PA111, PB711, PB821, PB822, PB824, etc.

In addition, as the resin-type dispersant used in the present invention, a resin-type dispersant having an acidic substituent is preferable, and among them, a resin-type dispersant having an aromatic carboxyl group is preferable because it prevents coloring after dispersion. The effect of re-agglomeration of the agent is particularly large. As a resin-type dispersing agent which has an aromatic carboxyl group, the resin-type dispersing agent containing following (S1) or (S2) is preferable.

(S1) A resin-type dispersant is a reaction product of a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and/or a tetracarboxylic dianhydride.

(S2) Resin-type dispersant, which is obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product of a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and/or a tetracarboxylic dianhydride polymer.

[Resin type dispersant (S1)]

The resin-type dispersant (S1) can be produced by known methods such as WO2008/007776 A, JP 2008-029901 A, and JP 2009-155406 A. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal, and it can be obtained, for example, in the form of a polymer obtained by making an ethylenically unsaturated monomer in the presence of the compound (q) having a hydroxyl group. (r) is polymerized. As a compound (q) which has a hydroxyl group, the compound which has a hydroxyl group and a thiol group in a molecule|numerator is preferable. Since the number of hydroxyl groups at the terminal is preferably plural, among them, the compound (q1) having two hydroxyl groups and one thiol group in the molecule can be preferably used.

That is, as a more preferable example, a polymer having two hydroxyl groups at one end can be obtained in the form of a polymer (p1), which has two hydroxyl groups and one thiol group in the molecule. It is obtained by polymerizing the ethylenically unsaturated monomer (r) containing the monomer (r1) in the presence of the compound (q1). The hydroxyl group of the hydroxyl group-containing polymer (p) reacts with the acid anhydride group of tricarboxylic acid anhydride and/or tetracarboxylic dianhydride to form an ester bond, and on the other hand, the acid anhydride ring is ring-opened to generate a carboxylic acid.

[Resin type dispersant (S2)]

The resin-type dispersant (S2) can be produced by known methods such as Japanese Patent Laid-Open No. 2009-155406, Japanese Patent Laid-Open No. 2010-185934, and Japanese Patent Laid-Open No. 2011-157416, for example, by It is obtained in the following manner, that is, in the presence of the reaction product of the hydroxyl group of the compound (q) having a hydroxyl group and the acid anhydride group of the tricarboxylic anhydride and/or the tetracarboxylic dianhydride, the ethylenically unsaturated monomer (r ) to aggregate. Among them, a polymer obtained by the following method, that is, the hydroxyl group of the compound (q1) having two hydroxyl groups and one thiol group in the molecule and tricarboxylic acid anhydride and/or tetracarboxylic acid dihydrate are preferable The ethylenically unsaturated monomer (r) including the monomer (r1) is polymerized in the presence of the reaction product of the acid anhydride group of the anhydride.

The difference between (S1) and (S2) is whether the introduction of the polymer moiety for the polymerization of the ethylenically unsaturated monomer (r) is carried out first or later. Although the molecular weight and the like may vary slightly depending on various conditions, they are theoretically the same as long as the raw materials and reaction conditions are the same.

The resin type dispersant is preferably used in an amount of about 5 parts by mass to about 200 parts by mass with respect to the total amount of the colorant, and more preferably about 5 parts by mass to about 100 parts by mass from the viewpoint of film-forming properties.

<Color Derivatives>

It is preferable that the coloring composition for color filters of this invention further contains a dye derivative. Pigment derivatives may also be included in azo pigments.

As the dye derivative used in the present invention, a known dye derivative in which the organic dye residue has an acidic group, a basic group, a neutral group, or the like can be used. For example, compounds having acidic functional groups such as sulfo group, carboxyl group and phosphoric acid group and amine salts thereof, or compounds having basic functional groups such as sulfonamido groups or tertiary amine groups at the end, compounds having phenyl or Compounds with neutral functional groups such as phthalimide alkyl groups. Examples of organic dyes include phthalocyanines such as diketopyrrolopyrrole-based pigments, copper phthalocyanine, zinc phthalocyanine, aluminum phthalocyanine, halogenated copper phthalocyanine, halogenated zinc phthalocyanine, halogenated aluminum phthalocyanine, and metal-free phthalocyanine. Cyanine pigments, anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavonoids, anthocyanidone, indanthrene, picanthrone, violanthrone, quinacridone-based pigments Pigments, dioxazine based pigments, perinone based pigments, perylene based pigments, thiazine indigo based pigments, triazine based pigments, benzimidazolone based pigments, indole based pigments such as benzisoindole, Isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo, disazo, polyazo Azo-based pigments such as nitrogen, etc.

More specifically, Japanese Patent Laid-Open No. 61-246261, Japanese Patent Laid-Open No. 63-264674, Japanese Patent Laid-Open No. 09-272812, Japanese Patent Laid-Open No. 10-245501, Japanese Patent Laid-Open No. 10-265697, Japanese Patent Laid-Open No. 11-199796, Japanese Patent Laid-Open No. 2001-172520, Japanese Patent Laid-Open No. 2001-220520, Japanese Patent Laid-Open No. 2002-201377, Japanese Patent Laid-Open No. 2003-165922, Japanese Patent Laid-Open No. 2003-168208, Japanese Patent Laid-Open No. 2003-171594, Japanese Patent Laid-Open No. 2004-217842, Japanese Patent Laid-Open No. 2005-213404, Japanese Patent Laid-Open No. 2006-291194, Japanese Patent Laid-Open No. 2007-079094, Japanese Patent Laid-Open No. 2007-226161, Japanese Patent Laid-Open No. 2007-314681, Japanese Patent Laid-Open No. 2007-314785, Japanese Patent Laid-Open No. 2008-31281, Japanese Patent Laid-Open No. 2009-57478, Pamphlet No. WO2009/025325, Pamphlet No. WO2009/081930, Japanese Patent Laid-Open No. 2011-162662, Pamphlet No. WO2011/052617, Japanese Patent JP 2012-172092 A, JP 2012-208329 A, JP 2012-226110 A, WO 2012/102399 pamphlet, JP 2014-5439 A, WO 2016/163351 pamphlet, Known dye derivatives described in Japanese Patent Laid-Open No. 2017-156397, Japanese Patent No. 5753266, etc. can be used alone or in combination of two or more. Furthermore, in these documents, pigment derivatives are sometimes described as derivatives, pigment derivatives, pigment dispersants, or simply as compounds, and the aforementioned organic pigment residues have an acidic group, a basic group, a neutral group, and the like. Compounds with functional groups such as radicals have the same meaning as pigment derivatives.

Among the dye derivatives used in the present invention, those having a basic substituent are preferred because the effect of suppressing the aggregation of the pigments is remarkable. Furthermore, as the organic dye residue, from the viewpoint of hue or contrast, a residue derived from a diketopyrrolopyrrole-based pigment, an anthraquinone-based pigment, a quinophthalone-based pigment, or an azo-based pigment is preferred.

<Surfactant>

Examples of the surfactant include: sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, alkylnaphthalenesulfonate Sodium, Sodium Alkyl Diphenyl Ether Disulfonate, Monoethanolamine Lauryl Sulfate, Triethanolamine Lauryl Sulfate, Ammonium Lauryl Sulfate, Monoethanolamine Stearate, Monoethanolamine of Styrene-Acrylic Acid Copolymer, Polyoxyethylene Alkane Anionic surfactants such as base ether phosphate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearic acid Nonionic surfactants such as esters and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts or their ethylene oxide adducts; alkyl dimethylaminoacetic acid Amphoteric surfactants such as alkylbetaines such as betaine and alkylimidazolines; these may be used alone or in combination of two or more, but are not necessarily limited to these.

When a surfactant is added, it is preferably 0.1 to 55 parts by mass, more preferably 0.1 to 45 parts by mass, relative to 100 parts by mass of the colorant. When the content of the surfactant is less than 0.1 part by mass, it is difficult to obtain the effect of addition, and when the content is more than 55 parts by mass, the dispersion may be affected by an excessive amount of the dispersant.

<Removal of coarse particles>

The coloring composition of the present invention is preferably obtained by centrifuging, filtering with a sintered filter or a membrane filter, etc., to separate coarse particles of 5 μm or more, preferably 1 μm or more, and more preferably 0.5 μm or more. Coarse particles and mixed dust are removed. Thus, it is preferable that a coloring composition does not contain particle|grains of 0.5 micrometer or more substantially. More preferably, it is 0.3 μm or less.

<Color filter>

Next, the color filter of the present invention will be described. The color filter of the present invention is a color filter with red filter segments, green filter segments, and blue filter segments on the substrate, and can also be further provided with magenta filter segments, A color filter of a cyan filter segment or a yellow filter segment, and the at least one filter segment is formed of the coloring composition of the present invention.

<Manufacturing method of color filter>

The color filter of the present invention can be produced by a printing method or a photolithography method. When the filter segment is formed by a printing method, patterning can be achieved only by repeatedly printing and drying the coloring composition prepared as a printing ink. Therefore, as a method for manufacturing a color filter, the cost is low and the mass productivity is excellent. Furthermore, with the development of printing technology, fine pattern printing with high dimensional accuracy and smoothness can be performed. In order to perform printing, it is preferable to set it as the composition which does not dry and harden the ink on a printing plate or a printing cloth (blanket). In addition, it is also important to control the fluidity of the ink on the printing press, and the viscosity of the ink can also be adjusted by using a dispersant or an extender pigment.

In the case of forming filter segments by photolithography, the coloring composition prepared as the solvent-developed or alkali-developed coloring resist material is prepared by spray coating, spin coating, or slit coating. Coating methods such as cloth and roll coating are applied on the transparent substrate so that the dry film thickness becomes 0.2 μm to 5 μm. For the film to be dried as needed, ultraviolet exposure is performed through a mask provided in a state of being in contact with or not in contact with the film and having a predetermined pattern. Then, it is immersed in a solvent or an alkaline developing solution, or sprayed with a developing solution by spraying or the like to remove the uncured portion to form a desired pattern, and then repeat the same operation for other colors to manufacture a color filter. Furthermore, in order to accelerate the polymerization of the coloring resist material, heating may be performed as necessary. According to the photolithography method, a color filter with higher precision than the above-mentioned printing method can be manufactured.

At the time of image development, an aqueous solution of sodium carbonate, sodium hydroxide, etc. is used as an alkali developing solution, and an organic base such as dimethylbenzylamine and triethanolamine may also be used. In addition, in the developing solution, an antifoaming agent or a surfactant may be added.

Furthermore, in order to improve the ultraviolet exposure sensitivity, after the above-mentioned coloring resist material is coated and dried, a water-soluble or alkali-soluble resin, such as polyvinyl alcohol or water-soluble acrylic resin, can be coated and dried to form an oxygen-resistant resin. After the resulting polymerization hindered the film, UV exposure was performed.

In addition to the above methods, the color filter of the present invention can also be produced by an electrodeposition method, a transfer method, an inkjet method, or the like, and the coloring composition of the present invention can be used for any method. Furthermore, the electrodeposition method is a method of manufacturing a color filter by using a transparent conductive film formed on a substrate to electrodeposit various colors on the transparent conductive film by electrophoresis of colloidal particles. Filter segments, thereby making color filters. In addition, the transfer method is a method of forming a filter segment on the surface of a releasable transfer substrate in advance, and transferring the filter segment to a desired substrate.

Before forming each color filter segment on a substrate such as a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited to these. In addition, thin film transistors (TFT; Thin Film Transistor) can also be pre-formed on the above-mentioned transparent substrate or reflective substrate, and then various color filter segments are formed. Moreover, on the color filter of this invention, an overcoat film, a transparent conductive film, etc. are formed as needed.

The dry film thickness of the filter segment and the black matrix is preferably 0.2 μm to 10 μm, more preferably 0.2 μm to 5 μm. When drying the coating film, a reduced pressure dryer, a convection oven, an IR (Infrared Radiation; infrared) oven, a hot plate, or the like can also be used.

Use a sealant to attach the color filter to the opposite substrate. After injecting the liquid crystal from the injection port provided in the sealing portion, the injection port is sealed. If necessary, a polarizing film or retardation film is attached to the outside of the substrate. This manufactures liquid crystal display panels.

The liquid crystal display panel can be used to use color filters such as Twisted Nematic (TN), Super Twisted Nematic (STN; Super Twisted Nematic), In-Plane Switching (IPS), Vertical Alignment (VA), Optical Compensation Bend (OCB), etc. LCD display mode for colorization.

As the transparent substrate, glass plates such as soda lime glass, low-alkali borosilicate glass, and alkali-free aluminoborosilicate glass, or resins such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate can be used. plate. In addition, on the surface of the glass plate or the resin plate, in order to drive the liquid crystal after the panel is formed, a transparent electrode made of indium oxide, tin oxide, or the like may be formed.

[Example]

Hereinafter, the present invention will be described based on Examples, but the present invention is not limited thereto. In addition, in the Example, "part" and "%" represent "mass part" and "mass %", respectively. In addition, "PGMAc" means propylene glycol monomethyl ether acetate.

<Weight Average Molecular Weight (Mw) of Resin>

The weight-average molecular weight (Mw) of the resin was obtained by using a TSKgel column (manufactured by Tosoh Corporation), and using a GPC (Gel Permeation Chromatography; Gel Permeation Chromatography) (Tosoh Corporation) equipped with an RI (Refractive Index; refractive index) detector. The weight average molecular weight (Mw) in terms of polystyrene measured using THF (Tetrahydrofuran; tetrahydrofuran) as a developing solvent.

<Identification method of azo pigment>

When identifying the azo pigment of the present invention, a MALDI (Matrix Assisted Laser Desorptioh Ionization; matrix-assisted laser desorption ionization) mass spectrometer autoflex III (hereinafter, referred to as TOF-MS (Time of Flight-Mass) manufactured by Bruker Daltonics) was used. Spectrometry; time-of-flight mass spectrometry)), identify the molecular ion peaks of the obtained mass spectrum consistent with the mass number obtained by calculation, and then use the 2400 CHN Element Analyser manufactured by PerkinElmer to identify each element obtained by The ratio is consistent with the theoretical value for identification.

<Contrast ratio of coating film>

The light emitted from the backlight unit for liquid crystal displays is polarized by the polarizing plate, and reaches the polarizing plate through the dried coating film of the coloring composition applied on the glass substrate. If the polarizing plate and the polarizing plane of the polarizing plate are parallel, the light passes through the polarizing plate, but when the polarizing planes are orthogonal, the light is blocked by the polarizing plate. However, when the light polarized by the polarizer passes through the dry coating film of the coloring composition, scattering due to pigment particles, etc. occurs, and deviation occurs in a part of the polarizing plane. When the polarizers are parallel, the amount of light that passes through the polarizers When the polarizers are orthogonal, part of the light passes through the polarizers. The transmitted light was measured as the brightness on the polarizing plate, and the ratio (contrast ratio) between the brightness when the polarizing plates were parallel and the brightness when the polarizing plates were perpendicular was calculated.

(contrast ratio) = (brightness when parallel) / (brightness when orthogonal)

In addition, as a luminance meter, a color luminance meter (“BM-5A” manufactured by Topcon Corporation) was used, and as a polarizing plate, a polarizing plate (“NPF-G1220DUN” manufactured by Nitto Denko Corporation) was used. In addition, in order to block unnecessary light during measurement, a black mask with a 1 cm square hole was placed on the measurement part.

First, the manufacturing method of the acrylic resin solution, the resin type dispersant solution, the coloring agent, the coloring composition, and the photosensitive coloring composition used in an Example, a manufacturing example, and a comparative example is demonstrated.

<Manufacturing method of acrylic resin solution>

(Preparation of Acrylic Resin Solution 1)

Add 196 parts of cyclohexanone to the reaction vessel equipped with a thermometer, a cooling tube, a nitrogen inlet tube, a drip tube and a stirring device on a separable four-necked flask, and the temperature was raised to 80°C. After the reaction vessel was replaced with nitrogen, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, p-cumylphenol ethylene oxide modified acrylate ( A mixture of 20.7 parts of "Aronix M110") and 1.1 parts of 2,2'-azobisisobutyronitrile manufactured by Toagosei Co., Ltd. After the dropwise addition, the reaction was continued for 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution were sampled, heated and dried at 180°C for 20 minutes, and the non-volatile components were measured. In the resin solution synthesized in advance, acetic acid methoxyl group was added in such a way that the non-volatile components became 20%. Propyl ester, Prepare Acrylic Resin Solution 1. The weight average molecular weight (Mw) was 26,000.

(Preparation of Acrylic Resin Solution 2)

Add 207 parts of cyclohexanone to the reaction vessel equipped with a thermometer, a cooling tube, a nitrogen inlet tube, a drip tube and a stirring device on a separable four-necked flask, and the temperature was raised to 80° C. After the reaction vessel was replaced with nitrogen, 20 parts of methacrylic acid, 20 parts of p-cumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 45 parts of methyl methacrylate, 20 parts of methyl methacrylate, 20 parts of A mixture of 8.5 parts of 2-hydroxyethyl acrylate and 1.33 parts of 2,2'-azobisisobutyronitrile. After the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, with respect to the entire amount of the obtained copolymer solution, the nitrogen gas was stopped, and the dry air was injected for 1 hour, and the mixture was stirred for 1 hour. After cooling to room temperature, 2-methacryloyl isocyanate was added dropwise at 70° C. for 3 hours. A mixture of 6.5 parts of ethyl ethyl ester (Karenz MOI manufactured by Showa Denko Co., Ltd.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone. After the dropwise addition, the reaction was continued for 1 hour to obtain a solution of an acrylic resin. After cooling to room temperature, sample about 2 parts of the resin solution, heat and dry it at 180°C for 20 minutes, measure the non-volatile content, and add cyclohexanone to the resin solution synthesized in advance so that the non-volatile content becomes 20%, Prepare Acrylic Resin Solution 2. The weight average molecular weight (Mw) was 18,000.

<Manufacturing method of resin type dispersant solution>

(Preparation of Resin Type Dispersant Solution 1)

In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of isobutyl methacrylate, and 20 parts of benzyl methacrylate were added, Replace with nitrogen. The inside of the reaction container was heated to 80 degreeC, the solution which melt|dissolved 0.1 part of 2,2'-azobisisobutyronitrile in 10 parts of 3-mercapto-1,2-propanediol was added, and it was made to react for 10 hours. 95% reaction was confirmed by solid content measurement. 20 parts of pyromellitic anhydride, 200.0 parts of methoxypropyl acetate, and 0.40 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 120° C. for 7 Hour. By measuring the acid value, it was confirmed that more than 98% of the acid anhydride was half-esterified to complete the reaction, and a polyester dispersant with an acid value of 77 mgKOH/g and a number average molecular weight of 8500 was obtained. To this polyester dispersant, methoxypropyl acetate was added so that the solid content in the measurement of the solid content might be 40% to obtain a resin-based dispersant solution 1 having an aromatic carboxyl group.

(Preparation of resin type dispersant solution 2)

In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of isobutyl methacrylate, and 20 parts of benzyl methacrylate were added, Replace with nitrogen. The inside of the reaction container was heated to 80 degreeC, the solution which melt|dissolved 0.1 part of 2,2'-azobisisobutyronitrile in 10 parts of 3-mercapto-1,2-propanediol was added, and it was made to react for 10 hours. 95% reaction was confirmed by solid content measurement. 36 parts of trimellitic anhydride, 200.0 parts of methoxypropyl acetate, and 0.40 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 120° C. for 7 hours . By measuring the acid value, it was confirmed that more than 98% of the acid anhydride was half-esterified to complete the reaction, and a polyester dispersant with an acid value of 109 mgKOH/g and a number average molecular weight of 8500 was obtained. To this polyester dispersant, methoxypropyl acetate was added so that the solid content in the measurement of the solid content would be 40% to obtain a resin-based dispersant solution 2 having an aromatic carboxyl group.

(Preparation of resin type dispersant solution 3)

In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 6.5 parts of 3-mercapto-1,2-propanediol, 4.0 parts of pyromellitic anhydride, 0.01 part of dimethylbenzylamine, and methoxyacetic acid were added. 41.8 parts of propyl propyl esters were replaced with nitrogen gas. The inside of the reaction vessel was heated to 100°C, and the reaction was carried out for 7 hours. After confirming that more than 98% of the acid anhydride was half-esterified by the measurement of the acid value, the temperature in the system was cooled to 70°C, and 67 parts of methyl methacrylate, 5.0 parts of methacrylic acid, and 16.0 parts of tert-butyl acrylate were added. , 10.0 parts of hydroxymethyl methacrylate and 2.0 parts of ethyl acrylate, 0.10 parts of 2,2'-azobisisobutyronitrile and 60.0 parts of methoxypropyl acetate were added and reacted for 10 hours. It was confirmed by solid content measurement that the polymerization progressed by 95%, and the reaction was completed to obtain a polyester dispersant having an acid value of 43 mgKOH/g and a number average molecular weight of 15,000. To this polyester dispersant, methoxypropyl acetate was added so that the solid content in the measurement of the solid content might become 40%, to obtain a resin-based dispersant solution 3 having an aromatic carboxyl group.

(Preparation of resin type dispersant solution 4)

In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 6.5 parts of 3-mercapto-1,2-propanediol, 4.0 parts of pyromellitic anhydride, 0.01 part of dimethylbenzylamine, and methoxyacetic acid were added. 41.8 parts of propyl propyl esters were replaced with nitrogen gas. The inside of the reaction vessel was heated to 100°C, and the reaction was carried out for 7 hours. After confirming that more than 98% of the acid anhydride was half-esterified by the measurement of the acid value, the temperature in the system was cooled to 70°C, and 67 parts of methyl methacrylate, 5.0 parts of methacrylic acid, and 16.0 parts of tert-butyl acrylate were added. , 10.0 parts of (3-ethyloxetan-3-yl) methyl methacrylate, 2.0 parts of ethyl acrylate, and 0.10 parts of 2,2'-azobisisobutyronitrile and methoxy acetate 60.0 parts of propyl esters were reacted for 10 hours. It was confirmed by solid content measurement that 95% of the polymerization progressed, the reaction was completed, and a polyester dispersant having an acid value of 47 mgKOH/g and a number average molecular weight of 15,000 was obtained. To this polyester dispersant, methoxypropyl acetate was added so that the solid content in the measurement of the solid content might become 40%, and a resin-based dispersant solution 4 having an aromatic carboxyl group was obtained.

<Method for producing dye derivative>

The production method and structure of the dye derivative used in the present invention are shown below. In addition, this invention is not limited to this.

(Manufacture of Pigment Derivative 1)

With reference to Synthesis Example 3 of Japanese Patent No. 5748665, the dye derivative 1 represented by the formula 5 was produced.

Formula 5

(Manufacture of Pigment Derivative 2)

With reference to Production Example 21 of Japanese Patent No. 4396778, the dye derivative 2 represented by Formula 6 was produced.

(Manufacture of Pigment Derivative 3)

With reference to Production Example 6 of Japanese Patent No. 4983061, the dye derivative 3 represented by the formula 7 was produced.

Formula 7

(Manufacture of Pigment Derivative 4)

With reference to Example 1 of Japanese Patent No. 5316690, the dye derivative 4 represented by the formula 8 was produced.

(Manufacture of Pigment Derivative 5)

16 parts of 5-nitroisophthalic acid and 1.0 part of N,N-dimethylformamide (DMF; N,N-Dimethylformamide) were dissolved in 110 parts of toluene. To this solution, 22.6 parts of thionium chloride was added dropwise over 25 minutes, and the mixture was refluxed at 110° C. for 1 hour to synthesize 5-nitroisophthalic acid dichloride. 38.0 parts of 4-amino-N-(3-(diethylamino)propyl)benzamide was dispersed in 90 parts of toluene, and the above-mentioned 5-nitrogen was added dropwise to the solution over 1 hour at room temperature. After isophthalic acid dichloride, the reaction was terminated by refluxing for 4 hours. After toluene was distilled off while neutralizing with 10% sodium carbonate aqueous solution, 28.0 parts of compounds represented by the following formula 9 were obtained by reslurrying with 3% NaOH aqueous solution, filtration, and drying.

Next, 25.0 parts of the compound represented by the above formula 9 was dissolved in 100 parts of N-methylpyrrolidone, and 32 parts of sodium hydrosulfide hydrate (containing 65% of sodium hydrosulfide) was added to the solution in 55 parts. After the aqueous solution obtained by adding water, the mixture was refluxed for 6 hours to obtain 20.0 parts of the base compound represented by the following formula 10.

20.0 parts of the base compound represented by the above formula 10 was dispersed in 200 parts of water, ice was added to adjust the temperature to 5°C, 20.0 parts of a 35% hydrochloric acid aqueous solution was added, and after stirring for 1 hour, 3.60 parts of sodium nitrite was added to the water. 11.0 parts of the prepared aqueous solution was stirred for 2 hours. Next, an aqueous solution consisting of 59.0 parts of an 80% aqueous acetic acid solution, 65.0 parts of a 25% aqueous sodium hydroxide solution, and 64.0 parts of water was added to prepare a diazonium salt aqueous solution. On the other hand, 18.7 parts of N-[2-methoxy-5-chlorophenyl]-3-hydroxy-2-naphthoamide and 53.5 parts of a 25% aqueous sodium hydroxide solution were dissolved in 340 parts of methanol to prepare Coupler solution.

This coupler solution was poured into the above-mentioned aqueous diazonium salt solution at 5°C for 30 minutes to carry out a coupling reaction. The pH at this time was 4.4. After stirring for 1 hour to confirm 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 35.8 parts of the dye derivative 5 represented by Formula 11.

(Manufacture of Pigment Derivative 6)

With reference to Production Example 3 of Japanese Patent No. 1863188, the dye derivative 6 represented by Formula 12 was produced.

Formula 12

<Manufacturing method of colorant>

(base compound)

The base compounds ([B-1] to [B-18]) used this time are listed in Table 1. Ph in the table represents a phenyl group.

(Production of Coupler Compound [C-1])

After mixing 167 parts of 3-hydroxy-2-naphthoic acid, 1500 parts of tetrahydrofuran, and 1 part of N,N-dimethylformamide, 221 parts of thionine chloride was added, and the mixture was stirred at room temperature for 1 hour to obtain Carboxylic chloride solution. Moreover, the solution which mixed 1000 parts of N-methylpyrrolidone and 48 parts of 1, 3- phenylenediamine was prepared in advance, and the carboxylate chloride solution was dripped over 30 minutes to this solution. At this time, dropwise addition was performed while maintaining the temperature of the reaction solution at 10° C. or lower. After the dropwise addition was completed, the mixture was stirred at room temperature for 2 hours, and the precipitated reactant was collected by filtration to obtain the target product. Furthermore, 196 parts of coupler compounds [C-1] were obtained by washing with 1000 parts of methanol and drying under reduced pressure (yield: 98.5%).

(Production of Coupler Compound [C-2] to Coupler Compound [C-70])

In place of the 48 parts of 1,3-phenylenediamine used in the production of the coupler compound [C-1], the diamines and parts by mass described in Table 2 were changed, and in addition to that, the mixture with the coupler compound [C-1] was carried out. Preparation of C-1] In the same manner, coupler compound [C-2] to coupler compound [C-70] were prepared.

<Manufacture of azo pigments>

[Example 1]

(Manufacture of Azo Pigment 1)

After adding 185 parts of base compound [B-1] to 1500 parts of N-methylpyrrolidone, 294 parts of 35% hydrochloric acid was added, and it cooled so that it might become -2 degreeC to 0 degreeC. After adding 208 parts of 25% sodium nitrite aqueous solution to this solution, it stirred for 30 minutes, maintaining at 0 degreeC to 5 degreeC, and prepared the diazonium solution. Furthermore, a coupler solution consisting of 167 parts of coupler compound [C-1], 316 parts of 25% sodium hydroxide solution, and 1500 parts of methanol was prepared. The prepared diazonium solution and the coupler solution were simultaneously added dropwise to 1000 parts of an acetic acid buffer solution of pH 5.4 over 10 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and further stirred while maintaining the temperature at 80° C. The precipitated reactant was collected by filtration, washed with hot water, and dried to obtain 343 parts of azo Pigment 1 (yield: 95.8%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 1.

[Example 2]

(Manufacture of Azo Pigment 2)

Except having used 169 parts of base compounds [B-2] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 1, the same operation as the manufacture of the azo pigment 1 was carried out to obtain 337 parts of azo pigment 2 (yield: 98.1%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 2.

[Example 3]

(Manufacture of Azo Pigment 3)

Except having used 210 parts of base compounds [B-3] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 1, the same operation as the manufacture of the azo pigment 1 was carried out to obtain 371 parts of azo pigment 3 (yield: 96.7%). Using the results of mass spectrometry analysis and elemental analysis by TOF-MS, it was identified as azo pigment 3.

[Example 4]

(Manufacture of Azo Pigment 4)

Except having used 181 parts of base compounds [B-4] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 1, the same operation as the manufacture of the azo pigment 1 was carried out to obtain 340 parts of azo pigment 4 (yield: 95.6%). Using the results of mass spectrometry analysis and elemental analysis by TOF-MS, it was identified as azo pigment 4.

[Example 5]

(Manufacture of Azo Pigment 5)

Except having used 222 parts of base compound [B-5] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 1, the same operation as the manufacture of the azo pigment 1 was carried out to obtain 384 parts of azo pigment 5 (yield: 97.1%). Using the results of mass spectrometry analysis and elemental analysis by TOF-MS, it was identified as azo pigment 5.

[Example 6]

(Manufacture of Azo Pigment 6)

Except having used 228 parts of base compound [B-6] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 1, the same operation as the manufacture of the azo pigment 1 was carried out to obtain 393 parts of azo pigment 6 (yield: 97.8%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 6.

[Example 7]

(Manufacture of Azo Pigment 7)

Except having used 124 parts of base compound [B-7] in place of 185 parts of base compound [B-1] used in manufacture of azo pigment 1, the same operation as that of manufacture of azo pigment 1 was carried out to obtain 287 parts of azo pigment 7 (yield: 96.2%). Using the results of mass spectrometry analysis and elemental analysis by TOF-MS, it was identified as azo pigment 7.

[Example 8]

(Manufacture of Azo Pigment 8)

Except having used 128 parts of base compounds [B-8] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 1, the same operation as the manufacture of the azo pigment 1 was carried out to obtain 296 parts of azo pigment 8 (yield: 97.9%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 8.

[Example 9]

(Manufacture of Azo Pigment 9)

Except having used 156 parts of base compound [B-9] instead of 185 parts of base compound [B-1] used in the manufacture of azo pigment 1, the same operation as that of manufacture of azo pigment 1 was carried out to obtain 322 parts of azo pigment 9 (yield: 97.7%). Using the results of mass spectrometry analysis and elemental analysis by TOF-MS, it was identified as azo pigment 9.

[Example 10]

(Manufacture of Azo Pigment 10)

Except having used 187 parts of base compounds [B-10] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 1, the same operation as the manufacture of the azo pigment 1 was carried out to obtain 357 parts of azo pigment 10 (yield: 98.9%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 10.

[Example 11]

(Manufacture of Azo Pigment 11)

Except having used 190 parts of base compound [B-11] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 1, the same operation as the manufacture of the azo pigment 1 was carried out to obtain 352 parts of azo pigment 11 (yield: 96.6%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 11.

[Example 12]

(Manufacture of Azo Pigment 12)

Except having used 240 parts of base compounds [B-12] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 1, the same operation as the manufacture of the azo pigment 1 was carried out to obtain 399 parts of azo pigment 12 (yield: 96.4%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 12.

[Example 13]

(Manufacture of Azo Pigment 13)

Except having used 207 parts of base compounds [B-13] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 1, the same operation as the manufacture of the azo pigment 1 was carried out to obtain 373 parts of azo pigment 13 (yield: 97.9%). Using the results of mass spectrometry analysis and elemental analysis by TOF-MS, it was identified as azo pigment 13.

[Example 14]

(Manufacture of Azo Pigment 14)

Except having used 241 parts of base compounds [B-14] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 1, the same operation as the manufacture of the azo pigment 1 was carried out to obtain 394 parts of azo pigment 14 (yield: 95.0%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 14.

[Example 15]

(Manufacture of Azo Pigment 15)

Except having used 215 parts of base compound [B-15] instead of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 1, the same operation as the manufacture of the azo pigment 1 was carried out to obtain 372 parts of azo pigment 15 (yield: 95.8%). Using the results of mass spectrometry analysis and elemental analysis of TOF-MS, it was identified as azo pigment 15.

[Example 16]

(Manufacture of Azo Pigment 16)

Except having used 233 parts of base compound [B-16] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 1, the same operation as the manufacture of the azo pigment 1 was carried out to obtain 390 parts of azo pigment 16 (yield: 96.0%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 16.

[Example 17]

(Manufacture of Azo Pigment 17)

Except having used 298 parts of base compound [B-17] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 1, the same operation as the manufacture of the azo pigment 1 was carried out to obtain 455 parts of azo pigment 17 (yield: 96.5%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 17.

[Example 18]

(Manufacture of Azo Pigment 18)

Except having used 415 parts of base compound [B-18] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 1, the same operation as the manufacture of the azo pigment 1 was carried out to obtain 567 parts of azo pigment 18 (yield: 96.5%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 18.

[Example 19]

(Manufacture of Azo Pigment 19)

The same operation as in the production of azo pigment 1 was carried out, except that 219 parts of the coupler compound [C-57] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 1, 396 parts of azo pigment 19 were obtained (yield: 96.4%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 19.

Azo Pigments 19

[Example 20]

(Manufacture of Azo Pigment 20)

Except having used 169 parts of base compounds [B-2] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 19, the same operation as the manufacture of the azo pigment 19 was carried out to obtain 390 parts of azo pigment 20 (yield: 98.7%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 20.

[Example 21]

(Manufacture of Azo Pigment 21)

Except having used 210 parts of base compound [B-3] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 19, the same operation as the manufacture of the azo pigment 19 was carried out to obtain 430 parts of azo pigment 21 (yield: 98.7%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 21.

[Example 22]

(Manufacture of Azo Pigment 22)

Except having used 181 parts of base compounds [B-4] instead of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 19, the same operation as the manufacture of the azo pigment 19 was carried out to obtain 397 parts of azo pigment 22 (yield: 97.4%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 22.

[Example 23]

(Manufacture of Azo Pigment 23)

222 parts of the base compound [B-5] was used in place of 185 parts of the base compound [B-1] used in the production of the azo pigment 19, and the same operation as in the production of the azo pigment 19 was carried out to obtain 433 parts of azo pigment 23 (yield: 96.7%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 23.

[Example 24]

(Manufacture of Azo Pigment 24)

228 parts of the base compound [B-6] was used in place of 185 parts of the base compound [B-1] used in the production of the azo pigment 19, and the same operation as in the production of the azo pigment 19 was carried out to obtain 435 parts of azo pigment 24 (yield: 95.8%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 24.

[Example 25]

(Manufacture of Azo Pigment 25)

In place of 185 parts of the base compound [B-1] used in the production of the azo pigment 19, except that 124 parts of the base compound [B-7] was used, the same operation as in the production of the azo pigment 19 was carried out to obtain 344 parts of azo pigment 25 (yield: 98.0%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 25.

[Example 26]

(Manufacture of Azo Pigment 26)

Except having used 128 parts of base compound [B-8] in place of 185 parts of base compound [B-1] used in the manufacture of azo pigment 19, the same operation as that of manufacture of azo pigment 19 was carried out to obtain 337 parts of azo pigment 26 (yield: 95.2%). Using the results of mass spectrometry analysis and elemental analysis by TOF-MS, it was identified as azo pigment 26.

[Example 27]

(Manufacture of Azo Pigment 27)

Except having used 156 parts of base compounds [B-9] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 19, the same operation as the manufacture of the azo pigment 19 was carried out to obtain 373 parts of azo pigment 27 (yield: 97.6%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 27.

[Example 28]

(Manufacture of Azo Pigment 28)

Except having used 187 parts of base compounds [B-10] in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 19, the same operation as the manufacture of the azo pigment 19 was carried out to obtain 393 parts of azo pigment 28 (yield: 95.1%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 28.

[Example 29]

(Manufacture of Azo Pigment 29)

Except having used 190 parts of base compound [B-11] in place of 185 parts of base compound [B-1] used in the manufacture of azo pigment 19, the same operation as that of manufacture of azo pigment 19 was carried out to obtain 405 parts of azo pigment 29 (yield: 97.4%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 29.

[Example 30]

(Manufacture of Azo Pigment 30)

240 parts of the base compound [B-12] was used in place of 185 parts of the base compound [B-1] used in the production of the azo pigment 19, and the same operation as in the production of the azo pigment 19 was carried out to obtain 456 parts of azo pigment 30 (yield: 97.8%). Using the results of mass spectrometry analysis and elemental analysis by TOF-MS, it was identified as azo pigment 30.

[Example 31]

(Manufacture of Azo Pigment 31)

207 parts of the base compound [B-13] was used in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 19, and the same operation as the manufacture of the azo pigment 19 was carried out to obtain 424 parts of azo pigment 31 (yield: 97.8%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 31.

[Example 32]

(Manufacture of Azo Pigment 32)

241 parts of the base compound [B-14] was used in place of 185 parts of the base compound [B-1] used in the production of the azo pigment 19, and the same operation as in the production of the azo pigment 19 was carried out to obtain 457 parts of azo pigment 32 (yield: 97.8%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 32.

Azo Pigments 32

[Example 33]

(Manufacture of Azo Pigment 33)

215 parts of the base compound [B-15] was used in place of 185 parts of the base compound [B-1] used in the production of the azo pigment 19, and the same operation as in the production of the azo pigment 19 was carried out to obtain 428 parts of azo pigment 33 (yield: 97.0%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 33.

[Example 34]

(Manufacture of Azo Pigment 34)

In place of 185 parts of the base compound [B-1] used in the production of the azo pigment 19, except that 233 parts of the base compound [B-16] was used, the same operation as in the production of the azo pigment 19 was carried out to obtain 445 parts of azo pigment 34 (yield: 97.0%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 34.

[Example 35]

(Manufacture of Azo Pigment 35)

Except that 298 parts of the base compound [B-17] was used in place of 185 parts of the base compound [B-1] used in the manufacture of the azo pigment 19, the same operation as the manufacture of the azo pigment 19 was carried out to obtain 500 parts of the base compound [B-17]. parts of azo pigment 35 (yield: 95.7%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 35.

[Example 36]

(Manufacture of Azo Pigment 36)

629 parts of azo pigment 36 (yield: 98.4%). Using the results of mass spectrometry analysis and elemental analysis by TOF-MS, it was identified as azo pigment 36.

[Example 37]

(Manufacture of Azo Pigment 37)

172 parts of the coupler compound [C-2] were used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 352 parts of azo pigment 37 were obtained (yield: 97.6%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 37.

[Example 38]

(Manufacture of Azo Pigment 38)

The same operation as in the production of azo pigment 4 was carried out, except that 172 parts of the coupler compound [C-3] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 357 parts of azo pigment 38 were obtained (yield: 98.9%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 38.

[Example 39]

(Manufacture of Azo Pigment 39)

177 parts of the coupler compound [C-4] was used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 354 parts of azo pigment 39 were obtained (yield: 96.7%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 39.

Azo Pigments 39

[Example 40]

(Manufacture of Azo Pigment 40)

177 parts of the coupler compound [C-5] was used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 357 parts of azo pigment 40 were obtained (yield: 97.6%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 40.

[Example 41]

(Manufacture of Azo Pigment 41)

182 parts of the coupler compound [C-6] were used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as in the manufacture of the azo pigment 4 was carried out, 355 parts of azo pigment 41 were obtained (yield: 95.8%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 41.

[Example 42]

(Manufacture of Azo Pigment 42)

The same operations as in the production of azo pigment 4 were performed, except that 193 parts of the coupler compound [C-7] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 366 parts of azo pigment 42 were obtained (yield: 95.9%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 42.

[Example 43]

(Manufacture of Azo Pigment 43)

The same operations as in the production of azo pigment 4 were carried out, except that 192 parts of the coupler compound [C-8] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 369 parts of azo pigment 43 were obtained (yield: 96.8%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 43.

[Example 44]

(Manufacture of Azo Pigment 44)

The same operations as in the production of azo pigment 4 were carried out, except that 197 parts of the coupler compound [C-9] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 381 parts of azo pigment 44 were obtained (yield: 98.7%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 44.

[Example 45]

(Manufacture of Azo Pigment 45)

178 parts of the coupler compound [C-10] was used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 356 parts of azo pigment 45 were obtained (yield: 97.0%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 45.

[Example 46]

(Manufacture of Azo Pigment 46)

178 parts of the coupler compound [C-11] was used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 355 parts of azo pigment 46 were obtained (yield: 97.0%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 46.

Azo Pigments 46

[Example 47]

(Manufacture of Azo Pigment 47)

The same operation as in the production of azo pigment 4 was carried out, except that 183 parts of the coupler compound [C-12] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 362 parts of azo pigment 47 were obtained (yield: 97.3%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 47.

[Example 48]

(Manufacture of Azo Pigment 48)

The same operation as in the production of azo pigment 4 was carried out, except that 198 parts of the coupler compound [C-13] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 382 parts of azo pigment 48 were obtained (yield: 98.9%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 48.

[Example 49]

(Manufacture of Azo Pigment 49)

173 parts of the coupler compound [C-14] were used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 355 parts of azo pigment 49 were obtained (yield: 98.4%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 49.

[Example 50]

(Manufacture of Azo Pigment 50)

In place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 179 parts of the coupler compound [C-15] was used, and the same operation as in the production of the azo pigment 4 was carried out, 358 parts of azo pigment 50 were obtained (yield: 97.6%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 50.

[Example 51]

(Manufacture of Azo Pigment 51)

179 parts of the coupler compound [C-16] were used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 350 parts of azo pigment 51 were obtained (yield: 95.3%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 51.

[Example 52]

(Manufacture of Azo Pigment 52)

176 parts of the coupler compound [C-17] were used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 360 parts of azo pigment 52 were obtained (yield: 98.7%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 52.

[Example 53]

(Manufacture of Azo Pigment 53)

184 parts of the coupler compound [C-18] were used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 367 parts of azo pigment 53 were obtained (yield: 98.6%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 53.

Azo Pigment 53

[Example 54]

(Manufacture of Azo Pigment 54)

The same operations as in the production of azo pigment 4 were carried out, except that 183 parts of the coupler compound [C-19] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 365 parts of azo pigment 54 were obtained (yield: 98.2%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 54.

[Example 55]

(Manufacture of Azo Pigment 55)

183 parts of the coupler compound [C-20] were used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 353 parts of azo pigment 55 were obtained (yield: 95.0%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 55.

[Example 56]

(Manufacture of Azo Pigment 56)

The same operations as in the production of azo pigment 4 were carried out, except that 183 parts of coupler compound [C-21] was used in place of 167 parts of coupler compound [C-1] used in the production of azo pigment 4, 365 parts of azo pigment 56 were obtained (yield: 98.3%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 56.

[Example 57]

(Manufacture of Azo Pigment 57)

In place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 197 parts of the coupler compound [C-22] was used, and the same operation as in the production of the azo pigment 4 was carried out, 379 parts of azo pigment 57 were obtained (yield: 98.4%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 57.

[Example 58]

(Manufacture of Azo Pigment 58)

The same operations as in the production of azo pigment 4 were carried out, except that 180 parts of the coupler compound [C-23] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 352 parts of azo pigment 58 were obtained (yield: 95.6%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 58.

[Example 59]

(Manufacture of Azo Pigment 59)

The same operations as in the production of azo pigment 4 were carried out, except that 196 parts of the coupler compound [C-24] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 369 parts of azo pigment 59 were obtained (yield: 95.9%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 59.

[Example 60]

(Manufacture of Azo Pigment 60)

174 parts of the coupler compound [C-25] were used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 353 parts of azo pigment 60 were obtained (yield: 97.6%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 60.

Azo Pigment 60

[Example 61]

(Manufacture of Azo Pigment 61)

The same operations as in the production of azo pigment 4 were carried out, except that 214 parts of the coupler compound [C-26] were used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 392 parts of azo pigment 61 were obtained (yield: 96.0%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 61.

[Example 62]

(Manufacture of Azo Pigment 62)

The same operations as in the production of azo pigment 4 were carried out, except that 192 parts of the coupler compound [C-27] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 362 parts of azo pigment 62 were obtained (yield: 95.1%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 62.

[Example 63]

(Manufacture of Azo Pigment 63)

180 parts of the coupler compound [C-28] was used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 364 parts of azo pigment 63 were obtained (yield: 98.8%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 63.

[Example 64]

(Manufacture of Azo Pigment 64)

In place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 187 parts of the coupler compound [C-29] were used, and the same operation as in the production of the azo pigment 4 was carried out, 366 parts of azo pigment 64 were obtained (yield: 97.5%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 64.

[Example 65]

(Manufacture of Azo Pigment 65)

The same operations as in the production of azo pigment 4 were performed, except that 194 parts of the coupler compound [C-30] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 366 parts of azo pigment 65 were obtained (yield: 95.8%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 65.

[Example 66]

(Manufacture of Azo Pigment 66)

196 parts of the coupler compound [C-31] was used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 374 parts of azo pigment 66 were obtained (yield: 97.3%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 66.

[Example 67]

(Manufacture of Azo Pigment 67)

The same operations as in the production of azo pigment 4 were carried out, except that 190 parts of the coupler compound [C-32] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 368 parts of azo pigment 67 were obtained (yield: 97.3%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 67.

Azo Pigment 67

[Example 68]

(Manufacture of Azo Pigment 68)

The same operations as in the production of azo pigment 4 were performed, except that 186 parts of the coupler compound [C-33] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 360 parts of azo pigment 68 were obtained (yield: 96.4%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 68.

[Example 69]

(Manufacture of Azo Pigment 69)

The same operations as in the production of azo pigment 4 were performed, except that 186 parts of the coupler compound [C-34] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 359 parts of azo pigment 69 were obtained (yield: 95.9%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 69.

[Example 70]

(Manufacture of Azo Pigment 70)

The same operation as in the production of azo pigment 4 was carried out, except that 212 parts of the coupler compound [C-35] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 393 parts of azo pigment 70 were obtained (yield: 98.2%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 70.

[Example 71]

(Manufacture of Azo Pigment 71)

In place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 178 parts of the coupler compound [C-36] was used, and the same operation as in the production of the azo pigment 4 was carried out, 352 parts of azo pigment 71 were obtained (yield: 95.9%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 71.

[Example 72]

(Manufacture of Azo Pigment 72)

189 parts of the coupler compound [C-37] was used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 373 parts of azo pigment 72 were obtained (yield: 98.8%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 72.

[Example 73]

(Manufacture of Azo Pigment 73)

The same operations as in the production of azo pigment 4 were carried out, except that 205 parts of the coupler compound [C-38] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 376 parts of azo pigment 73 were obtained (yield: 95.6%). Using the results of mass spectrometry analysis and elemental analysis by TOF-MS, it was identified as azo pigment 73.

[Example 74]

(Manufacture of Azo Pigment 74)

178 parts of the coupler compound [C-39] was used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 358 parts of azo pigment 74 were obtained (yield: 97.8%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 74.

Azo Pigment 74

[Example 75]

(Manufacture of Azo Pigment 75)

218 parts of the coupler compound [C-40] were used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 401 parts of azo pigment 75 were obtained (yield: 98.8%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 75.

[Example 76]

(Manufacture of Azo Pigment 76)

The same operation as in the production of azo pigment 4 was carried out, except that 183 parts of the coupler compound [C-41] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 367 parts of azo pigment 76 were obtained (yield: 98.7%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 76.

[Example 77]

(Manufacture of Azo Pigment 77)

185 parts of the coupler compound [C-42] was used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 356 parts of azo pigment 77 were obtained (yield: 95.3%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 77.

[Example 78]

(Manufacture of Azo Pigment 78)

The same operations as in the production of azo pigment 4 were performed, except that 191 parts of the coupler compound [C-43] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 372 parts of azo pigment 78 were obtained (yield: 98.0%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 78.

[Example 79]

(Manufacture of Azo Pigment 79)

The same operation as in the production of azo pigment 4 was carried out, except that 211 parts of the coupler compound [C-44] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 388 parts of azo pigment 79 were obtained (yield: 97.2%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 79.

[Example 80]

(Manufacture of Azo Pigment 80)

The same operations as in the production of azo pigment 7 were carried out, except that 172 parts of the coupler compound [C-2] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, 301 parts of azo pigment 80 were obtained (yield: 98.9%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 80.

[Example 81]

(Manufacture of Azo Pigment 81)

The same operations as in the production of azo pigment 7 were carried out, except that 172 parts of the coupler compound [C-3] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, 298 parts of azo pigment 81 were obtained (yield: 98.0%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 81.

[Example 82]

(Manufacture of Azo Pigment 82)

The same operation as in the production of azo pigment 7 was carried out, except that 192 parts of coupler compound [C-8] was used in place of 167 parts of coupler compound [C-1] used in the production of azo pigment 7, 317 parts of azo pigment 82 were obtained (yield: 98.0%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 82.

[Example 83]

(Manufacture of Azo Pigment 83)

The same operation as in the production of azo pigment 7 was carried out, except that 178 parts of the coupler compound [C-11] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, 300 parts of azo pigment 83 were obtained (yield: 96.8%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 83.

[Example 84]

(Manufacture of Azo Pigment 84)

The same operations as in the production of azo pigment 7 were carried out, except that 180 parts of the coupler compound [C-23] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, 307 parts of azo pigment 84 were obtained (yield: 98.6%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 84.

[Example 85]

(Manufacture of Azo Pigment 85)

The same operations as in the production of azo pigment 7 were carried out, except that 185 parts of the coupler compound [C-42] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, 309 parts of azo pigment 85 were obtained (yield: 98.6%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 85.

Azo Pigment 85

[Example 86]

(Manufacture of Azo Pigment 86)

The same operations as in the production of azo pigment 7 were carried out, except that 191 parts of the coupler compound [C-43] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, 317 parts of azo pigment 86 were obtained (yield: 98.4%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 86.

[Example 87]

(Manufacture of Azo Pigment 87)

The same operation as in the production of azo pigment 7 was carried out, except that 195 parts of coupler compound [C-45] was used in place of 167 parts of coupler compound [C-1] used in the production of azo pigment 4, 375 parts of azo pigment 87 were obtained (yield: 97.7%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 87.

Azo Pigment 87

[Example 88]

(Manufacture of Azo Pigment 88)

The same operations as in the production of azo pigment 4 were carried out, except that 200 parts of the coupler compound [C-46] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 373 parts of azo pigment 88 were obtained (yield: 96.0%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 88.

[Example 89]

(Manufacture of Azo Pigment 89)

The same operations as in the production of azo pigment 4 were carried out, except that 211 parts of the coupler compound [C-47] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 388 parts of azo pigment 89 were obtained (yield: 97.3%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 89.

[Example 90]

(Manufacture of Azo Pigment 90)

The same operations as in the production of azo pigment 4 were carried out, except that 251 parts of the coupler compound [C-48] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 422 parts of azo pigment 90 were obtained (yield: 96.1%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 90.

[Example 91]

(Manufacture of Azo Pigment 91)

The same operations as in the production of azo pigment 4 were performed except that 261 parts of the coupler compound [C-49] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 445 parts of azo pigment 91 were obtained (yield: 98.9%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 91.

[Example 92]

(Manufacture of Azo Pigment 92)

The same operations as in the production of azo pigment 4 were carried out, except that 263 parts of the coupler compound [C-50] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 437 parts of azo pigment 92 were obtained (yield: 96.9%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 92.

[Example 93]

(Manufacture of Azo Pigment 93)

The same operations as in the production of azo pigment 4 were carried out, except that 223 parts of the coupler compound [C-51] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 396 parts of azo pigment 93 were obtained (yield: 96.2%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 93.

[Example 94]

(Manufacture of Azo Pigment 94)

The same operation as in the production of azo pigment 4 was carried out, except that 229 parts of the coupler compound [C-52] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 409 parts of azo pigment 94 were obtained (yield: 97.9%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 94.

[Example 95]

(Manufacture of Azo Pigment 95)

The same operation as in the production of azo pigment 4 was carried out, except that 244 parts of the coupler compound [C-53] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 417 parts of azo pigment 95 were obtained (yield: 96.3%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 95.

[Example 96]

(Manufacture of Azo Pigment 96)

The same operation as in the production of azo pigment 4 was carried out, except that 201 parts of the coupler compound [C-54] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 382 parts of azo pigment 96 were obtained (yield: 98.1%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 96.

Azo Pigment 96

[Example 97]

(Manufacture of Azo Pigment 97)

207 parts of the coupler compound [C-55] was used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 383 parts of azo pigment 97 were obtained (yield: 96.9%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 97.

[Example 98]

(Manufacture of Azo Pigment 98)

206 parts of the coupler compound [C-56] was used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 383 parts of azo pigment 98 were obtained (yield: 97.3%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 98.

[Example 99]

(Manufacture of Azo Pigment 99)

The same operations as in the production of azo pigment 4 were carried out, except that 229 parts of the coupler compound [C-58] were used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 411 parts of azo pigment 99 were obtained (yield: 98.4%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 99.

[Example 100]

(Manufacture of Azo Pigment 100)

The same operations as in the production of azo pigment 4 were carried out, except that 229 parts of the coupler compound [C-59] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 400 parts of azo pigment 100 were obtained (yield: 95.8%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 100.

[Example 101]

(Manufacture of Azo Pigment 101)

The same operations as in the production of azo pigment 4 were carried out, except that 270 parts of the coupler compound [C-60] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 441 parts of azo pigment 101 were obtained (yield: 96.4%). Using the results of mass spectrometry analysis and elemental analysis by TOF-MS, it was identified as azo pigment 101.

[Example 102]

(Manufacture of Azo Pigment 102)

The same operation as in the production of azo pigment 4 was carried out, except that 245 parts of the coupler compound [C-61] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 421 parts of azo pigment 102 were obtained (yield: 97.3%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 102.

[Example 103]

(Manufacture of Azo Pigment 103)

The same operations as in the production of azo pigment 4 were carried out, except that 232 parts of the coupler compound [C-62] were used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 405 parts of azo pigment 103 were obtained (yield: 96.3%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 103.

Azo Pigment 103

[Example 104]

(Manufacture of Azo Pigment 104)

The same operations as in the production of azo pigment 4 were carried out, except that 231 parts of the coupler compound [C-63] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 399 parts of azo pigment 104 were obtained (yield: 96.3%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 104.

[Example 105]

(Manufacture of Azo Pigment 105)

The same operations as in the production of azo pigment 4 were carried out, except that 241 parts of the coupler compound [C-64] were used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 423 parts of azo pigment 105 were obtained (yield: 98.4%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 105.

[Example 106]

(Manufacture of Azo Pigment 106)

The same operation as in the production of azo pigment 4 was carried out, except that 281 parts of the coupler compound [C-65] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 456 parts of azo pigment 106 were obtained (yield: 97.1%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 106.

[Example 107]

(Manufacture of Azo Pigment 107)

In place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 212 parts of the coupler compound [C-66] was used, and the same operation as in the production of the azo pigment 4 was carried out, 395 parts of azo pigment 107 were obtained (yield: 98.7%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 107.

[Example 108]

(Manufacture of Azo Pigment 108)

211 parts of the coupler compound [C-67] was used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 390 parts of azo pigment 108 were obtained (yield: 97.7%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 108.

Azo Pigment 108

[Example 109]

(Manufacture of Azo Pigment 109)

The same operation as in the production of azo pigment 4 was carried out, except that 225 parts of the coupler compound [C-68] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 400 parts of azo pigment 109 were obtained (yield: 96.9%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 109.

[Example 110]

(Manufacture of Azo Pigment 110)

The same operation as in the production of azo pigment 4 was carried out, except that 230 parts of the coupler compound [C-69] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, 407 parts of azo pigment 110 were obtained (yield: 97.4%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 110.

[Example 111]

(Manufacture of Azo Pigment 111)

237 parts of the coupler compound [C-70] were used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 4, and the same operation as the manufacture of the azo pigment 4 was carried out, 409 parts of azo pigment 111 were obtained (yield: 96.0%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 111.

Azo Pigment 111

[Example 112]

(Manufacture of Azo Pigment 112)

200 parts of the coupler compound [C-46] was used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 7, and the same operation as the manufacture of the azo pigment 7 was carried out, 320 parts of azo pigment 112 were obtained (yield: 96.4%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 112.

[Example 113]

(Manufacture of Azo Pigment 113)

211 parts of the coupler compound [C-47] was used in place of 167 parts of the coupler compound [C-1] used in the manufacture of the azo pigment 7, and the same operation as the manufacture of the azo pigment 7 was carried out, 329 parts of azo pigment 113 were obtained (yield: 96.0%). Using the results of mass spectrometry and elemental analysis by TOF-MS, it was identified as azo pigment 113.

[Example 114]

(Manufacture of Azo Pigment 114)

The same operations as in the production of azo pigment 7 were carried out, except that 251 parts of the coupler compound [C-48] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, 374 parts of azo pigment 114 were obtained (yield: 97.6%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 114.

[Example 115]

(Manufacture of Azo Pigment 115)

The same operations as in the production of azo pigment 7 were carried out, except that 201 parts of the coupler compound [C-54] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, 319 parts of azo pigment 115 were obtained (yield: 95.7%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 115.

[Example 116]

(Manufacture of Azo Pigment 116)

The same operation as in the production of azo pigment 7 was carried out, except that 206 parts of the coupler compound [C-56] was used in place of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, 330 parts of azo pigment 116 were obtained (yield: 97.7%). Using the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 116.

[Example 117]

(Manufacture of Azo Pigment 117) Miniaturization Step of Azo Pigment 4

80 parts of azo pigment 4, 800 parts of sodium chloride, and 90 parts of diethylene glycol were added to a 1-gallon kneader made of stainless steel (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60° C. for 6 hours, and subjected to salt milling treatment. The obtained kneaded product was poured into 3 liters of warm water, stirred for 1 hour while heating to 70° C. to form a slurry, and after repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was heated to 80° C. After drying all day and night, 78 parts of azo pigment 117 were obtained.

[Example 118]

(Manufacture of Azo Pigment 118) Miniaturization Step of Azo Pigment 22

80 parts of azo pigments 22, 800 parts of sodium chloride, and 90 parts of diethylene glycol were added to a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60° C. for 6 hours, and subjected to salt milling. The obtained kneaded product was poured into 3 liters of warm water, stirred for 1 hour while heating to 70° C. to form a slurry, and after repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was heated to 80° C. After drying all day and night, 78 parts of azo pigment 118 were obtained.

[Example 119 to Example 124]

(Manufacture of Azo Pigment 120 to Azo Pigment 125)

In the production of the azo pigment 117, the same procedure as the azo pigment 117 was carried out, except that the azo pigment 4 and the pigment derivatives were changed to the types and ratios shown in Table 4-2 instead of the azo pigment 4. , azo pigment 120 to azo pigment 125 were obtained.

[Example 125 to Example 130]

(Manufacture of Azo Pigment 126 to Azo Pigment 131)

In the production of the azo pigment 118, the same procedure as the azo pigment 118 was carried out, except that the azo pigment 22 and the pigment derivatives were changed to the types and ratios shown in Table 4-2 instead of the azo pigment 22. , azo pigments 126 to 131 were obtained.

[Production Example 1]

(Manufacture of Azo Pigment 119)

With reference to Japanese Patent Laid-Open No. 2014-160160, the following azo pigment 119 was synthesized.

[Production Example 2 to Production Example 13]

<Manufacture of other pigments>

(Manufacture of Red Colorant 1 (RCP-1): PR254)

100 parts of commercially available CI Pigment Red 254 (PR254) ("Irgazin Red D3656 HD" manufactured by BASF Corporation), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd.) company), kneaded at 60°C for 6 hours, and subjected to salt milling. The obtained kneaded product was poured into 3 liters of warm water, stirred for 1 hour while heating to 70° C. to form a slurry, and after repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was heated to 80° C. After drying all day and night, 98 parts of red colorant 1 (RCP-1) were obtained. The average primary particle size was 33 nm.

(Manufacture of Red Colorant 2 (RCP-2): PR177)

Manufacture of CI Pigment Red 254 ("Irgazin Red D3656 HD" manufactured by BASF Corporation) to CI Pigment Red 177 (PR177) ("Cinilex Red SR3C" manufactured by CINIC Corporation), and the manufacture of Red Colorant 1 In the same way, 97 parts of red colorant 2 (RCP-2) were obtained. The average primary particle size was 37 nm.

(Manufacture of Red Colorant 3 (RCP-3): PR242)

Manufacture of CI Pigment Red 254 ("Irgazin Red D3656 HD" manufactured by BASF Corporation) to CI Pigment Red 242 (PR242) ("Sandorin Scarlet 4RF" manufactured by Clariant Corporation), and the manufacture of Red Colorant 1 In the same way, 98 parts of red colorant 3 (RCP-3) were obtained. The average primary particle size was 39 nm.

(Manufacture of Red Colorant 4 (RCP-4): PR269)

Changed CI Pigment Red 254 ("Irgazin Red D3656 HD" manufactured by BASF Corporation) to CI Pigment Red 269 (PR269) ("Permanent Carmine 3810" manufactured by Sanyo Color Co., Ltd.), and other than that, with red colorant Production of 1 was carried out in the same manner to obtain 98 parts of red colorant 4 (RCP-4). The average primary particle size was 35 nm.

(Manufacture of Red Colorant 5 (RCP-5): Brominated Diketopyrrolopyrrole Pigment Formula (4))

In a stainless steel reaction vessel with a reflux tube, under a nitrogen atmosphere, add 200 parts of tertiary amyl alcohol dehydrated by molecular sieves and 140 parts of sodium tertiary amyl alkoxide, and heat to 100°C while stirring to prepare an alcoholate solution. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask, heated to 90° C. while stirring, and dissolved to prepare a solution of these mixtures. While vigorously stirring the heated solution of the mixture, it was slowly added dropwise to the above-mentioned alcoholate solution heated at 100°C over 2 hours at a constant rate. After the dropwise addition, heating and stirring were continued at 90° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole-based compound. Furthermore, 600 parts of methanol, 600 parts of water, and 304 parts of acetic acid were added to the reaction container with a glass outer jacket, and it cooled to -10 degreeC. To the cooled mixture, a high-speed stirring disperser was used to rotate a shear disk with a diameter of 8 cm at 4000 rpm, and the base of the above-obtained diketopyrrolopyrrole compound cooled to 75° C. was gradually added to the mixture in small amounts. metal salt solution. At this time, the temperature of the mixture consisting of methanol, acetic acid, and water was cooled so that the temperature of the mixture was always kept below -5°C, and the addition rate of the alkali metal salt of the diketopyrrolopyrrole compound at 75°C was adjusted. , one side lasted about 120 minutes and gradually added a small amount. After the alkali metal salt was added, red crystals were precipitated to form a red suspension. Next, the obtained red suspension was washed with an ultrafiltration apparatus at 5° C., and then separated by filtration to obtain a red paste. The paste was redispersed in 3500 parts of methanol cooled to 0°C to prepare a suspension with a methanol concentration of about 90%, and stirred at 5°C for 3 hours, followed by particle granulation and washing with crystal transfer. Next, it was filtered and separated using an ultrafiltration machine, and the obtained aqueous paste of the diketopyrrolopyrrole-based compound was dried at 80° C. for 24 hours and pulverized to obtain dibromide represented by the formula (4). 150.8 parts of ketopyrrolopyrrole pigments.

100 parts of the brominated diketopyrrolopyrrole pigment represented by the formula (4) obtained above, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) , kneaded at 60°C for 6 hours, and performed salt milling treatment. The obtained kneaded product was poured into 3 liters of warm 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 heated to 80° C. After drying all day and night, 98 parts of red colorant 5 (RCP-5) were obtained. The average primary particle size was 45 nm.

(Manufacture of Yellow Colorant 1 (YCP-1): PY138)

500 parts of quinophthalone-based yellow pigment CI Pigment Yellow 138 (“Paliotol Yellow L0962-HD” manufactured by BASF), 500 parts of sodium chloride, and 250 parts of diethylene glycol were added to a stainless steel 1-gallon kneader (Inoue). manufactured by Seisakusho Co., Ltd.), and kneaded at 120° C. for 8 hours. Next, the kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70° C. to form a slurry, and after repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was heated to 80° C. After drying all day and night, 490 parts of yellow colorant 1 (YCP-1) were obtained. The average primary particle size was 63 nm.

(Manufacture of Yellow Colorant 2 (YCP-2): PY139)

500 parts of isoindoline-based yellow pigment CI Pigment Yellow 139 (“Paliotol Yellow L1820” manufactured by BASF Corporation), 500 parts of sodium chloride, and 250 parts of diethylene glycol were added to a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd.) company), kneaded at 120°C for 8 hours. Next, the kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70° C. to form a slurry, and after repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was heated to 80° C. After drying all day and night, 510 parts of yellow colorant 2 (YCP-2) were obtained. The average primary particle size was 68 nm.

(Manufacture of Yellow Colorant 3 (YCP-3): PY150)

500 parts of azo-based yellow pigment CI Pigment Yellow 150 (“Hostaperm Yellow HN4G” manufactured by Clariant Corporation), 500 parts of sodium chloride, and 250 parts of diethylene glycol were added to a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd. ) and kneaded at 120°C for 8 hours. Next, the kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70° C. to form a slurry, and after repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was heated to 80° C. After drying all day and night, 500 parts of yellow colorant 3 (YCP-3) were obtained. The average primary particle size was 60 nm.

(Production of Yellow Colorant 4 (YCP-4): Quinophthalone Compound (b))

To 200 parts of methyl benzoate, 40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalene dicarboxylic anhydride, and 154 parts of benzoic acid were added, and the mixture was heated to 180° C. and stirred for 4 hours. Furthermore, after cooling to room temperature, the reaction mixture was put into 5440 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain 116 parts of the quinophthalone compound (c). As a result of mass spectrometry analysis by TOF-MS, it was identified as the quinophthalone compound (c).

Quinophthalone compound (c)

Furthermore, using the quinophthalone compound (c) as a raw material, the compound (c-2) was obtained according to the synthesis method described in Japanese Patent Laid-Open No. 2008-81566.

To 300 parts of methyl benzoate, 100 parts of compound (c-2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added, and the mixture was heated to 180° C. and reacted for 4 hours. The formation of the quinophthalone compound (b) and the disappearance of the raw material compound (c-2) were confirmed by TOF-MS. Furthermore, after cooling to room temperature, the reaction mixture was put into 3510 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol and dried to obtain 120 parts of quinophthalone compound (b). As a result of mass spectrometry analysis by TOF-MS, it was identified as the quinophthalone compound (b).

Quinophthalone compound (b)

500 parts of the quinophthalone compound (b) obtained above, 500 parts of sodium chloride, and 250 parts of diethylene glycol were added to a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 120° C. for 8 hours. Next, the kneaded product was poured into 5 liters of warm water, stirred for 1 hour while heating to 70° C. to form a slurry, and after repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was heated to 80° C. After drying all day and night, 480 parts of yellow colorant 4 (YCP-4) were obtained. The average primary particle size was 62 nm.

(Manufacture of Green Colorant 1: PG58)

Phthalocyanine-based green pigment CI Pigment Green 58 ("FASTOGEN GREEN A110" manufactured by DIC Co., Ltd.) 200 parts, 1,400 parts of sodium chloride, and 360 parts of diethylene glycol were added to a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd. production), kneaded at 80° C. for 6 hours. Next, the kneaded product was poured into 8,000 parts of warm water, stirred for 2 hours while heating to 80° C. to make a slurry, and the sodium chloride was removed by repeated filtration and water washing. After adding diethylene glycol, it was dried at 85° C. all day and night to obtain 190 parts of green colorant 1. The average primary particle size was 69 nm.

(Production of blue colorant 1: PB15:6)

200 parts of phthalocyanine-based blue pigment CI Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by Toyocolor Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were added to a 1-gallon kneader made of stainless steel (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 80°C for 6 hours. Next, the kneaded product was poured into 8,000 parts of warm water, stirred for 2 hours while heating to 80° C. to form a slurry, and after repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was heated to 85° C. After drying all day and night, 190 parts of blue colorant 1 were obtained. The average primary particle size was 74 nm.

(Production of Purple Colorant 1: PV23)

200 parts of dioxazine-based purple pigment CI Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyocolor Co., Ltd.), 1,400 parts of sodium chloride, and 360 parts of diethylene glycol were added to a stainless steel 1-gallon kneader (Inoue). manufactured by Seisakusho Co., Ltd.), and kneaded at 80°C for 6 hours. Next, the kneaded product was poured into 8,000 parts of warm water, stirred for 2 hours while heating to 80° C. to form a slurry, and after repeated filtration and washing to remove sodium chloride and diethylene glycol, the mixture was heated to 85° C. After drying for one day and night, 190 parts of purple colorant 1 were obtained. The average primary particle size was 69 nm.

The results of mass spectrometry and elemental analysis of the azo pigments produced in the above Examples 1 to 116 are shown in Tables 3 and 4. In addition, Table 4 shows the evaluation results of the average primary particle diameter in all the produced pigments.

<Manufacturing method of coloring composition>

[Example 201]

(Production of coloring composition (RM-1))

The following mixture was stirred and mixed so as to be uniform, and then dispersed for 3 hours with a pigment dispersing mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) using zirconia beads with a diameter of 0.5 mm. , and filtered through a filter with a pore size of 5.0 μm to prepare a coloring composition (RM-1) with a non-volatile content of 20% by mass.

Red colorant (RP-1): 12.0 parts

Acrylic resin solution 1: 19.2 parts

Propylene glycol monomethyl ether acetate (PGMAc): 60.8 parts

Acid resin type dispersant solution ("Disperbyk-110" (solid content 52%) manufactured by BYK-Chemie): 8.0 parts

[Example 202 to Example 330, Comparative Example 1]

(Coloring composition (RM-2 to 131)

Hereinafter, coloring compositions (RM-2 to 131) were prepared in the same manner as the coloring composition (RM-1) except that the compositions were changed to the compositions shown in Table 5 and Table 5-2.

[Example 331]

(Production of coloring composition (RM-132))

After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, disperse it with a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan) for 3 hours, and then use a pore size 5.0 It filtered with the filter of micrometer, and produced the coloring composition (RM-132) whose nonvolatile content is 20 mass %.

Red colorant (RP-4): 12.0 parts

Acrylic resin solution 1: 19.2 parts

Propylene glycol monomethyl ether acetate (PGMAc): 60.5 parts

Acid resin type dispersant solution ("SOLSPERSE-55000" (solid content 50%) manufactured by Lubrizol Corporation): 8.3 parts

[Example 332]

(Production of Coloring Composition (RM-133))

After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, disperse it with a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan) for 3 hours, and then use a pore size 5.0 It filtered with the filter of micrometer, and produced the coloring composition (RM-133) whose nonvolatile content is 20 mass %.

Red colorant (RP-4): 12.0 parts

Acrylic resin solution 1: 19.2 parts

Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts

Alkaline resin type dispersant solution (“Disperbyk-2000” (solid content 40%) manufactured by BYK-Chemie): 10.4 parts

[Example 333]

(Production of coloring composition (RM-134))

After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, disperse it with a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan) for 3 hours, and then use a pore size 5.0 It filtered with the filter of μm, and produced the coloring composition (RM-134) whose non-volatile content is 20 mass %.

Red colorant (RP-4): 12.0 parts

Acrylic resin solution 1: 40.0 parts

Propylene glycol monomethyl ether acetate (PGMAc): 48.0 parts

[Example 334]

(Production of coloring composition (RM-135))

After stirring and mixing the following mixture in a uniform manner, using zirconia beads with a diameter of 0.5 mm, dispersed for 3 hours by a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan), using a pore diameter of 5.0 It filtered with the filter of micrometer, and produced the coloring composition (RM-135) whose nonvolatile content is 20 mass %.

Red colorant (RP-4): 12.0 parts

Acrylic resin solution 1: 19.2 parts

Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts

Acidic resin type dispersant solution (resin type dispersant solution 1): 10.4 parts

[Example 335 to Example 337]

(Coloring composition (RM-136 to 138))

Hereinafter, coloring compositions (RM-136 to 138) were prepared in the same manner as the coloring composition (RM-135) except that the composition was changed to the composition shown in Table 5-3.

[Example 338]

(Coloring composition (RM-139)

A coloring composition (RM-139) was prepared in the same manner as the coloring composition (RM-132) except that the red coloring agent (RP-4) was changed to the red coloring agent (RP-22).

[Example 339]

(Coloring composition (RM-140))

A coloring composition (RM-140) was prepared in the same manner as the coloring composition (RM-133) except that the red coloring agent (RP-4) was changed to the red coloring agent (RP-22).

[Example 340]

(Coloring composition (RM-141))

A coloring composition (RM-141) was prepared in the same manner as the coloring composition (RM-134) except that the red coloring agent (RP-4) was changed to the red coloring agent (RP-22).

[Example 341]

(Coloring composition (RM-142))

A coloring composition (RM-142) was prepared in the same manner as the coloring composition (RM-135) except that the red coloring agent (RP-4) was changed to the red coloring agent (RP-22).

[Example 342 to Example 344]

(Coloring composition (RM-143 to 145))

Hereinafter, coloring compositions (RM-143 to 145) were prepared in the same manner as the coloring composition (RM-142) except that the composition was changed to the composition shown in Table 5-3.

[Example 345]

(Production of coloring composition (RM-146))

After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, disperse it with a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan) for 3 hours, and then use a pore size 5.0 It filtered with the filter of micrometer, and produced the coloring composition (RM-146) whose non-volatile content is 20 mass %.

Red Colorant (RP-4): 10.8 parts

Pigment Derivative 1: 1.2 parts

Acrylic resin solution 1: 19.2 parts

Propylene glycol monomethyl ether acetate (PGMAc): 60.8 parts

Acid resin type dispersant solution (“Disperbyk-110” manufactured by BYK-Chemie): 8.0 parts

[Example 346 to Example 350, Example 353 to Example 358]

(Coloring composition (RM-147 to 151, 154 to 159))

Hereinafter, coloring compositions (RM-147 to 151, 154 to 159) were prepared in the same manner as the coloring compositions (RM-146) except that the compositions were changed to the compositions shown in Table 5-4.

[Example 351]

(Production of coloring composition (RM-152))

After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, disperse it with a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan) for 3 hours, and then use a pore size 5.0 It filtered with the filter of micrometer, and produced the coloring composition (RM-152) whose nonvolatile content is 20 mass %.

Red Colorant (RP-4): 10.8 parts

Pigment Derivative 1: 1.2 parts

Acrylic resin solution 1: 19.2 parts

Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts

Acidic resin type dispersant solution (resin type dispersant solution 1): 10.4 parts

[Example 352, Example 359, Example 360]

(Coloring composition (RM-153, 160, 161))

Hereinafter, the coloring compositions (RM-153, 160, 161) were prepared in the same manner as the coloring compositions (RM-152) except that the compositions were changed to the compositions shown in Table 5-4.

[Comparative Example 2]

(Coloring composition (RCM-2): PR177)

After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, disperse it with a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan) for 3 hours, and then use a pore size 5.0 It filtered with the filter of micrometer, and produced the coloring composition (RCM-2) whose nonvolatile content is 20 mass %.

Red Colorant 2 (RCP-2) (PR177): 12.0 parts

Acrylic resin solution 1: 36.4 parts

Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts

Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts

[Comparative Example 3]

(Coloring composition (RCM-4): PR269)

After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, disperse it with a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan) for 3 hours, and then use a pore size 5.0 It filtered with the filter of micrometer, and produced the coloring composition (RCM-4) whose nonvolatile content is 20 mass %.

Red Colorant 4 (RCP-4) (PR269): 12.0 parts

Acrylic resin solution 1: 36.4 parts

Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts

Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts

(Coloring composition (RCM-1): PR254)

After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, disperse it with a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan) for 3 hours, and then use a pore size 5.0 It filtered with the filter of micrometer, and produced the coloring composition (RCM-1) whose nonvolatile content is 20 mass %.

Red Colorant 1 (RCP-1) (PR254): 12.0 parts

Acrylic resin solution 1: 36.4 parts

Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts

Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts

(Coloring composition (RCM-3): PR242)

After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, disperse it with a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan) for 3 hours, and then use a pore size 5.0 It filtered with the filter of micrometer, and produced the coloring composition (RCM-3) whose nonvolatile content is 20 mass %.

Red Colorant 3 (RCP-3) (PR242): 12.0 parts

Acrylic resin solution 1: 36.4 parts

Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts

Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts

(Coloring composition (RCM-5): Formula (4))

After stirring and mixing the following mixture in a uniform manner, using zirconia beads with a diameter of 0.5 mm, dispersed for 3 hours by a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan), using a pore diameter of 5.0 It filtered with the filter of micrometer, and produced the coloring composition (RCM-5) whose nonvolatile content is 20 mass %.

Red colorant 5 (RCP-5) (formula (4)): 12.0 parts

Acrylic resin solution 1: 36.4 parts

Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts

Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts

(Coloring composition (YCM-1): PY138)

After stirring and mixing the following mixture in a uniform manner, using zirconia beads with a diameter of 0.5 mm, dispersed for 3 hours by a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan), using a pore diameter of 5.0 It filtered with the filter of micrometer, and produced the coloring composition (YCM-1) whose nonvolatile content is 20 mass %.

Yellow Colorant 1 (YCP-1) (PY138): 12.0 parts

Acrylic resin solution 1: 36.4 parts

Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts

Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts

(Coloring composition (YCM-2): PY139)

After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, disperse it with a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan) for 3 hours, and then use a pore size 5.0 It filtered with the filter of micrometer, and produced the coloring composition (YCM-2) whose nonvolatile content is 20 mass %.

Yellow Colorant 2 (YCP-2) (PY139): 12.0 parts

Acrylic resin solution 1: 36.4 parts

Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts

Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts

(Coloring composition (YCM-3): PY150)

After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, disperse it with a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan) for 3 hours, and then use a pore size 5.0 It filtered with the filter of micrometer, and produced the coloring composition (YCM-3) whose nonvolatile content is 20 mass %.

Yellow Colorant 3 (YCP-3) (PY150): 12.0 parts

Acrylic resin solution 1: 36.4 parts

Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts

Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts

(Coloring composition (YCM-4): Quinophthalone compound (b))

After stirring and mixing the following mixture so that it becomes uniform, using zirconia beads with a diameter of 0.5 mm, disperse it with a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan) for 3 hours, and then use a pore size 5.0 It filtered with the filter of micrometer, and produced the coloring composition (YCM-4) whose nonvolatile content is 20 mass %.

Yellow colorant 4 (YCP-4) quinophthalone compound (b)): 12.0 parts

Acrylic resin solution 1: 36.4 parts

Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts

Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts

(Evaluation of coloring compositions)

The heat resistance, light resistance, foreign matter in the coating film, and storage stability of the obtained coloring composition and the coating film produced using the coloring composition were evaluated by the following methods. The evaluation results are shown in Table 5.

(heat resistance evaluation)

Using a spin coater, the coloring composition was coated on a glass substrate with a thickness of 100 mm×100 mm and a thickness of 1.1 mm so that the dry film thickness would be 2.0 μm, then dried at 70° C. for 20 minutes, and then heated at 230° C. for 60 minutes. And it stood to cool, and the coating-film board|substrate (one aspect of a color filter) was produced by this. The chromaticity ([L ^* (1), a ^* (1), b ^* (1 )]). ^{Furthermore, as a heat resistance test, the chromaticity ([L*} (2), a ^* (2), b ^* (2)]) under the C light source was measured by heating at 250° C. for 1 hour, and the following formula was used to obtain The color difference ΔEab ^* was evaluated on the following four levels.

△Eab ^* =√((L ^* (2)-L ^* (1)) ² +(a ^* (2)-a ^* (1)) ² +(b ^* (2)-b ^* (1)) ² )

◎: △Eab ^* less than 1.0 (extremely good)

○: △Eab ^* is 1.0 or more and less than 2.5 (good)

△: △Eab ^* is 2.5 or more and less than 5.0 (defective)

×: △Eab ^* is 5.0 or more (extremely poor)

(Lightfastness Evaluation)

In the same manner as in the heat resistance evaluation, a coated substrate was prepared, and the chromaticity ([L ^* (1), a) under C light source was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). ^* (1), b ^* (1)]). Next, a UV cut filter (“COLORED OPTICAL GLASS L38” manufactured by HOYA) was attached to the substrate, and a 470W/m ² xenon lamp was used to irradiate UV light for 100 hours, and then the chromaticity under the C light source was measured ([ L ^* (2), a ^* (2), b ^{* (2)]), the color difference ΔEab* was} obtained by the above-mentioned calculation formula, and the evaluation was performed according to the same criteria as heat resistance.

(Evaluation of foreign matter in coating film)

Using a spin coater, the coloring composition was coated on a glass substrate with a thickness of 100 mm×100 mm and a thickness of 1.1 mm so that the dry film thickness was 2.0 μm, then dried at 70° C. for 20 minutes, and then heated at 230° C. for 60 minutes. And it was left to cool, whereby a coated substrate was produced. For the evaluation, surface observation was performed using a metal microscope "BX60" manufactured by Olympus Systems. The magnification is set to 500 times, and the number of particles that can be observed in any 5 fields of view is counted by transmission. Evaluation was performed according to the following four levels.

◎: The number of foreign objects is less than 5 (extremely good)

○: The number of foreign objects is 5 or more and less than 10 (good)

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

×: The number of foreign objects is 60 or more (extremely defective)

(Storage Stability Test Method)

Using an E-type viscometer (TUE-20L type manufactured by Toki Sangyo Co., Ltd.), the viscosity of the coloring composition at 25° C. was measured at a rotational speed of 20 rpm. The viscosity change rate (%) (=(viscosity after storage at 40°C for 7 days - initial value) was calculated based on the initial viscosity of the coloring composition on the production day and the viscosity measured after 7 days of storage in a constant temperature room at 40°C. Viscosity)/initial viscosity×100), and the storage stability was evaluated according to the following criteria.

◎: The viscosity change rate is less than 10% (extremely good)

○: The viscosity change rate is 10% or more and less than 20% (good)

△: The viscosity change rate is 20% or more and less than 50% (defective)

×: The viscosity change rate is 50% or more (extremely poor)

As shown in Table 5, the coloring composition using the coloring agent of the present invention showed favorable results in terms of the heat resistance of the coating film, light resistance, foreign matter in the coating film, and storage stability. In particular, when compared with the coloring composition using the azo pigment 119 (Comparative Example 1), the dispersion is more stable due to the higher-order steric hindrance of the pigment, and thus the quality improvement can be seen. In addition, by using together a resin-based dispersant or a pigment derivative having an aromatic carboxylic acid in particular, it is possible to obtain excellent heat resistance and light resistance, as well as good foreign matter in the coating film and good storage stability.

<The manufacturing method of the photosensitive coloring composition for color filters>

[Example 401]

(Photosensitive Coloring Composition (RR-1))

After stirring and mixing the following mixture (total 100 parts) so that it may become uniform, it filtered with the filter of 1.0 micrometers of pore diameters, and obtained the photosensitive coloring composition (RR-1).

Coloring composition (RM-1): 23.0 parts

Coloring composition (RCM-1): 27.0 parts

Acrylic resin solution 2: 7.5 parts

Photopolymerizable monomer ("Aronix M-402" manufactured by Toa Gosei Corporation): 2.0 parts

dipentaerythritol hexaacrylate

Photopolymerization initiator ("OXE-02" manufactured by BASF Corporation): 1.5 parts

Ethanone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime)

Cyclohexanone: 39.0 parts

[Example 402 to Example 567, Comparative Example 4 to Comparative Example 13]

(Photosensitive Coloring Composition (RR-2 to 177))

As shown in Table 6, the photosensitive coloring composition (RR-2 to 177) was obtained in the same manner as the photosensitive coloring composition (RR-1) except that the type and ratio of the coloring composition were adjusted.

<Evaluation of the photosensitive coloring composition for color filters>

The evaluation of the brightness, the contrast ratio, and the film thickness of the obtained photosensitive coloring composition was performed by the following method. The evaluation results are shown in Table 6. In addition, Table 7 shows the evaluation of the migration property.

(Evaluation of Brightness)

The obtained photosensitive coloring composition was coated on a glass substrate, dried at 70°C for 20 minutes, and then heated at 230°C for 60 minutes to obtain the chromaticity of the substrate under C light source as x=0.683, y=0.313 Coated substrate. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

(Evaluation of Contrast Ratio (CR))

The contrast ratio was determined using the substrate whose brightness was measured.

(Evaluation of film thickness)

The film thickness was measured using the substrate whose brightness was measured. For the measurement of the film thickness, a surface profiler DEKTAK150 (manufactured by ULVAC ES) was used.

(Evaluation of migration properties)

Using a slit die coater, the photosensitive coloring composition for a color filter was coated on a glass substrate, and then pre-baked for 2 minutes on a 90° C. hot plate to form a coating film with a thickness of 2.4 μm. Then, after cooling the substrate on which the coating film was formed to room temperature, using a high-pressure mercury lamp, through a striped mask, using radiation having wavelengths of 365 nm, 405 nm and 436 nm, the coating film was exposed to an exposure amount of ^{1,000 J/m 2 .} Expose. After alkali development, washing with ultrapure water, and post-baking at 230° C. for 20 minutes, red stripe-shaped pixels were formed on the substrate. Next, the transmittance (T1) at 520 nm was measured on the glass substrate at a distance of only 8 μm from the red stripe-shaped pixels. Furthermore, after applying the acrylic resin solution 2 on the substrate using a slit die coater, prebaking was performed for 2 minutes on a hot plate at 90° C. to form a coating film having a thickness of 2.5 μm. Furthermore, post-baking was performed at 230 degreeC for 20 minutes. Next, the transmittance (T2) of 520 nm on the glass substrate only 8 micrometers away from the red stripe-shaped pixel was measured. The difference between T1 and T2 was set to ΔT (%), and the evaluation was performed on the following four levels. It can be said that the smaller the ΔT value, the less the decrease in brightness caused by the color transfer to the adjacent other color filter segments, and the more inhibited the dye migration.

◎: △T less than 0.5% (very good)

○: ΔT is 0.5% or more and less than 1.0% (good)

△: △T is 1.0% or more and less than 3.0% (defective)

×: △T is 3.0% or more (extremely poor)

From the results in Table 6, it is apparent that the examples using the colorant of the present invention have excellent brightness and become thin films. In particular, by using in place of C.I. Pigment Red 177, C.I. Pigment Red 269, or Azo Pigment 119, which were previously used as bluish pigments, a remarkable effect was confirmed.

Furthermore, as shown in Table 7, it was confirmed that the coloring composition using the coloring agent of the present invention had good migration properties.

<The manufacturing method of the green and blue photosensitive coloring composition for color filters>

(Green photosensitive coloring composition 1: PG58/PY138)

After stirring and mixing the following mixture so as to become uniform, using zirconia beads with a diameter of 0.5 mm, disperse for 5 hours with a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan), and then use a pore size of 5.0 Filter with a μm filter to prepare a green pigment dispersion with a non-volatile content of 20% by mass.

Green Colorant 1 (C.I. Pigment Green 58): 12.0 parts

Acrylic resin solution 1: 36.4 parts

Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts

Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts

After stirring and mixing the following mixture so as to become uniform, using zirconia beads with a diameter of 0.5 mm, disperse for 5 hours with a pigment dispersing mill (“Minimodel M-250 MKII” manufactured by Eiger Japan), and then use a pore size of 5.0 Filtration was carried out with a filter of μm to prepare a yellow pigment dispersion with a non-volatile content of 20% by mass.

Yellow Colorant 1 (C.I. Pigment Yellow 138): 12.0 parts

Acrylic resin solution 1: 36.4 parts

Propylene glycol monomethyl ether acetate (PGMAc): 50.2 parts

Acid resin type dispersant solution ("Disperbyk-110" manufactured by BYK-Chemie): 1.4 parts

Next, after stirring and mixing the mixture of the following composition so that it may become uniform, it filtered with the filter of 1 micrometer of pore diameters, and produced the green photosensitive coloring composition 1.

Green Pigment Dispersion: 32.0 parts

Yellow Pigment Dispersion: 18.0 parts

Acrylic resin solution 2: 7.5 parts

Photopolymerizable monomer ("Aronix M-402" manufactured by Toa Gosei Co., Ltd.): 2.0 parts

dipentaerythritol hexaacrylate

Photopolymerization initiator ("OXE-02" manufactured by BASF Corporation): 1.5 parts

Ethanone, 1-[9-ethyl-6-(2-methylbenzyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime)

Cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition 1:PB15:6/PV23)

Except that the green colorant 1 (CI Pigment Green 58) was changed to the blue colorant 1 (CI Pigment Blue 15:6), in the same manner as the green pigment dispersion, a nonvolatile content of 20% by mass was obtained. Blue pigment dispersion.

In the same manner as the green pigment dispersion, except that the green colorant 1 (CI Pigment Green 58) was changed to the purple colorant 1 (CI Pigment Violet 23), a purple pigment dispersion having a nonvolatile content of 20% by mass was obtained body.

Next, 32.0 parts of green pigment dispersions and 50.0 parts of yellow pigment dispersions in total of 18.0 parts were replaced by 46.0 parts of blue dispersions and 50.0 parts of total violet dispersions of 4.0 parts, and coloring with green photosensitivity. In the same manner as the composition 1, a blue photosensitive coloring composition 1 was obtained.

<Production and Evaluation of Color Filters>

Using a slit die coater, the red photosensitive coloring composition (RR-1) was coated on the glass substrate formed with the black matrix, and then pre-baked with a 90°C hot plate for 2 minutes to form a coating film . Then, after cooling the substrate on which the coating film was formed to room temperature, using a high-pressure mercury lamp, through a striped mask, using radiation having wavelengths of 365 nm, 405 nm and 436 nm, the coating film was exposed to an exposure amount of ^{1,000 J/m 2 .} Expose. After alkali development, washing with ultrapure water, and post-baking at 230° C. for 20 minutes, red stripe-shaped pixels were formed on the substrate.

Next, by the same method, the green stripe-shaped pixel was formed in the vicinity of the red stripe-shaped pixel using the green photosensitive coloring composition 1. Furthermore, using the blue photosensitive coloring composition 1, blue stripe-shaped pixels adjacent to the red and green pixels were similarly formed.

Next, a protective film is formed using a photocurable resin composition on a pixel composed of three colors of red, green, and blue. In this way, an RGB3 color filter with high brightness and excellent various resistance can be produced.

Claims (9)

An azo pigment, consisting of a compound represented by the following general formula (1) or general formula (2);

In the general formula (1), R ₁ represents a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, or an aryloxy group which may have a substituent; R ₂ and R ₃ each independently represent hydrogen atom, an alkyl group that may have a substituent, or a phenyl group that may have a substituent; X ₁ to X ₄ each independently represent a hydrogen atom, an alkyl group that may have a substituent group, an alkoxy group that may have a substituent group, a hydroxyl group, cyano, nitro, carboxyl, sulfo, or halogen atoms;

In the general formula (2), R ₄ represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted aryloxy group; R ₅ and R ₆ each independently represent hydrogen atom, an alkyl group which may have a substituent group, or a phenyl group which may have a substituent group; X ₅ to X ₁₂ each independently represent a hydrogen atom, an alkyl group which may have a substituent group, an alkoxy group which may have a substituent group, a hydroxyl group, A cyano group, a nitro group, or a halogen atom; A represents a direct bond or a divalent linking group; the aforementioned divalent linking group is an alkylene group that may have a substituent, -O-, -S-, -CO-, - SO ₂ -, -COO-, -CONH-, or -SO ₂ NH-. A colorant for color filters, comprising the azo pigment according to claim 1. A coloring composition for a color filter, comprising at least a colorant and a binder resin, wherein the colorant is the colorant for a color filter as described in claim 2. The coloring composition for color filters of Claim 3 which further contains the resin-type dispersing agent which has an acidic substituent. The coloring composition for color filters according to claim 4, wherein the resin-type dispersant having an acidic substituent is a resin-type dispersant having an aromatic carboxyl group. The coloring composition for a color filter according to claim 3, further comprising a dye derivative including a dye derivative having a basic substituent. The coloring composition for a color filter according to claim 3, wherein the colorant further comprises a colorant selected from the group consisting of CI Pigment Red 254, CI Pigment Red 242, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, At least one of the group consisting of the yellow pigment represented by the general formula (3) and the brominated diketopyrrolopyrrole pigment; the general formula (3)

In the general formula (3), Z ₁ to Z ₁₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, -SO ₃ H, -COOH, and monovalent to trivalent metal salts of these acidic groups, alkylammonium salts, optionally substituted phthalimidomethyl, or optionally substituted sulfasulfonate ; _{Adjacent groups in Z 1} to Z ₄ and/or Z ₁₀ to Z ₁₃ may be integrated to form an aromatic ring which may have a substituent. The coloring composition for color filters according to claim 3, further comprising a photopolymerizable monomer. A color filter including a filter segment on a substrate, the filter segment being formed of the coloring composition for a color filter according to any one of Claims 3 to 8.