TW201917175A - Azo pigment, coloring material for color filter, coloring composition for color filter, and color filter having high brightness and contrast and high tinting strength - Google Patents

Abstract

A subject 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 small film-coating foreign matter, good storage stability, high brightness and contrast, and the film thickness gets thinner when the same color is expressed. The above subject is solved by an azo pigment which is composed of a compound represented by the following formula (1) or formula (2). [In the formula (1), R1 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. R2 and R3 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent.], [In the formula (2), R4 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. R5 and R6 each independently represent a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. X5 to X12 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group, a hydroxyl group, a cyano group, a nitro group, or a halogen atom which may have a substituent. A represents a direct bond or a divalent linking. The aforementioned divalent linking group is an alkyl group which may have a substituent, -O-, -S-, -CO-, -SO2-, -COO-, -CONH-, or -SO2NH- ].

Description

   Azo pigments, colorants for color filters, coloring compositions for color filters, and color filters   

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

The liquid crystal display device is a display device that displays a liquid crystal layer sandwiched between two polarizing plates to control the degree of polarization of light passing through the first polarizing plate and regulate the amount of light passing through the second polarizing plate. In a liquid crystal display device, a type using Twisted Nematic (TN) liquid crystal has become the mainstream. Other representative liquid crystal display devices include an in-plane switching (IPS) method in which a pair of electrodes are provided on a single-sided substrate and an electric field is applied in a direction parallel to the substrate. Vertical alignment (VA; Vertical Alignment) method for anisotropic nematic liquid crystals, and optically compensated bends (OCB; Optically Compensated Bend) for optical compensation by orthogonalizing the optical axes of uniaxial retardation films to each other Methods, etc., and each method has been put into practical use.

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

The color filter is composed of the following color filters: a color filter in which two or more fine band (striped) filter segments of two or more different colors are arranged on the surface of a transparent substrate such as glass in parallel or crosswise Light filters, or color filters in which fine filter segments are arranged in a fixed horizontal and vertical arrangement. The filter segments are as fine as several micrometers to hundreds of micrometers, and are arranged neatly in a predetermined arrangement for each hue.

Generally, in a color liquid crystal display device, a transparent electrode is formed on a color filter by evaporation or sputtering to drive the liquid crystal, and an alignment film is formed on the transparent electrode to make the liquid crystal Orientation in a fixed direction. In order to fully obtain the performance of the transparent electrodes and alignment films, the transparent electrodes and alignment films must be formed at a high temperature of generally 200 ° C or higher, preferably 230 ° C or higher. Therefore, currently, as a method for manufacturing a color filter, a method called a pigment dispersion method has become mainstream, and this method uses a pigment having excellent light resistance and heat resistance as a colorant.

Examples of quality items required for color filters include brightness and contrast ratio. If a color filter with a low contrast ratio is used, the degree of polarization controlled by the liquid crystal will be confusing, light leakage will occur when light must be blocked (OFF state), or transmitted light attenuation will occur when light must be transmitted (ON state). , Resulting in blurred images. Therefore, in order to realize a high-quality liquid crystal display device, high contrast is indispensable.

In addition, if a color filter with a low brightness is used, the light transmittance is low, so it becomes a dim picture. In order to obtain a bright picture, the number of backlights used as a light source must be increased. Therefore, from the viewpoint of suppressing an increase in power consumption, it is a trend to increase the brightness of color filters. Furthermore, since color liquid crystal devices are gradually used in televisions, computer monitors, and the like as described above, the requirements for high brightness, high contrast, and high reliability of color filters have also increased.

For red filter segments that are one of the three primary colors (red, green, blue; RGB) of a color filter substrate, diketopyrrolopyrrole pigments, anthraquinone pigments, and perylene pigments are generally used alone or in combination. A pigment having excellent heat resistance is used as a colorant.

Among the above pigment types, CI Pigment Red 254, which is a diketopyrrolopyrrole pigment, is used as the main pigment from the viewpoint of brightness, and CI Pigment Red 177, which is an anthraquinone pigment, is used from the viewpoint of contrast. As the main pigment. Among them, 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. Therefore, the addition of C.I. Pigment Red 177 has the disadvantage of causing a decrease in brightness. Therefore, it is desirable to develop C.I. Pigment Red 177, which is excellent in brightness, as an alternative material.

In recent years, in order to achieve high brightness and high tinting power, 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, the pigment's affinity for solvents, or the acidity of the pigment surface is different from CI Pigment Red 254 or CI Pigment Red 177, etc., so it also has poor dispersibility, flowability, and poor storage stability, and further has heat resistance and light resistance. It is also disadvantageous in that it cannot obtain a practical color filter. In addition, azo pigments such as C.I. Pigment Red 269 sometimes have a problem of reduced brightness due to color transfer to adjacent other color filter segments, and have high requirements for migration properties.

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 pigment described in Patent Document 3 as the main pigment. However, the methods of Patent Documents 1 to 3 cannot obtain sufficient brightness, and further improvement is required.

[Prior technical literature]

[Patent Literature]

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

Patent Document 2: Japanese Patent Publication No. 2007-533802.

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

The object of the present invention is to provide a colored composition for a color filter, which not only has excellent fastness properties such as heat resistance and light resistance, has few foreign matter on the coating film, has good storage stability, has low migration, but also has high brightness and contrast, and exhibits high performance. The film thickness becomes thinner for the same color.

The inventors of the present invention have conducted diligent research, and as a result, have found that the use of an azo pigment having a specific structure in a colorant for a color filter can solve the above-mentioned problems and complete 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 alkyl group which may have a substituent, an alkoxy group which may have a substituent, 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 aspect of this invention is a coloring agent for color filters containing the said azo pigment.

An embodiment of the present invention relates to a coloring composition for a color filter, which contains at least a coloring agent and a binder resin, and the coloring agent is the coloring agent for the color filter.

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

An embodiment of the present invention relates to the coloring composition for a color filter, wherein the resin-based dispersant having an acidic substituent is a resin-based dispersant having an aromatic carboxyl group.

Moreover, the aspect of this invention is the said coloring composition for color filters which further contains a pigment derivative, and this pigment derivative contains the pigment derivative which has a basic substituent.

An embodiment of the present invention relates to the coloring composition for a color filter, wherein the colorant further comprises a member selected from the group consisting of CI Pigment Red 254, CI Pigment Red 242, CI Pigment Yellow 138, CI Pigment Yellow 139, and CI. Pigment yellow 150, at least one of the group consisting of 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, alkyl ammonium salts, phthalimide imide methyl groups which may have a substituent, or sulfamidines which may have a substituent base.

The 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, the aspect of this invention is 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 having a filter segment on a substrate, the filter segment being formed of the coloring composition for a color filter.

According to the present invention, an 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 is excellent in not only fastness such as heat resistance and light resistance, but also a coating film. Few foreign matter, good storage stability, low migration, high brightness and contrast, thin film thickness 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) acrylfluorenyl", "(meth) acryl", "(meth) acryl", "(meth) acrylate", or "(formyl In the case of "methacryl)", unless otherwise specified, it means "acryl and / or methacryl", respectively, "acryl and / or methacryl", "acryl and / or methyl "Methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamine". In addition, "C.I." listed 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 a compound represented by general formula (1) or general formula (2)" may be abbreviated as "pigment" and "colorant for color filters" The description is simply referred to as "colorant".

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.

Furthermore, each of a plurality of R ₁ , R _2, and R _{3 in} the general formula (1) may be the same as or different from each other.

Examples of the "halogen atom" in R ₁ include fluorine, bromine, chlorine, and iodine. Among these, chlorine is preferred.

Examples of the "alkyl group which may have a substituent" in R ₁ include methyl, ethyl, n-propyl, isopropyl, n-butyl, third butyl, isobutyl, third pentyl, 2-ethylhexyl, stearyl, chloromethyl, trichloromethyl, trifluoromethyl, 2-methoxyethyl, 2-chloroethyl, 2-nitroethyl, cyclopentyl, cyclo Hexyl, dimethylcyclohexyl, etc. Among these, methyl and trifluoromethyl are preferred.

Examples of the "alkoxy group which may have a substituent" in R ₁ include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, n-octyloxy, and 2-ethyl Hexyloxy, trifluoromethoxy, cyclohexyloxy, stearyloxy, 2- (diethylamino) ethoxy, etc. Among these, methoxy and trifluoromethyl are preferred Of these, methoxy is particularly preferred.

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

Examples of the "alkyl group which may have a substituent" in R ₂ and R ₃ include methyl, ethyl, n-propyl, isopropyl, n-butyl, third butyl, isobutyl, and third 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, third butyl, isobutyl, 2- Hydroxyethyl.

Examples of the substituent of the "phenyl group which may have a substituent" in R ₂ and R ₃ include a halogen atom in R ₁ , an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and In addition to the aryloxy group having a substituent, a hydroxyl group, an amine group, -NR ₇ R ₈ , a sulfo group, -SO ₂ NR ₉ R ₁₀ , -COOR ₁₁ , -CONR ₁₂ R ₁₃ , nitrate, etc. can also be mentioned. And cyano.

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

X ₁ to X _{4 is,} as "the group may have a substituent alkoxy", and in R ₁ 'may have a substituent group of alkoxy group "meaning the same.

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 alkyl group which may have a substituent, an alkoxy group which may have a substituent, 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-.

Furthermore, each of a plurality of R ₄ , R _5, and R _{6 in} the general formula (2) may be the same as or different from each other.

In R ₄ , "halogen atom", "alkyl group which may have substituent", "alkoxy group which may have substituent", and "aryloxy group which may have substituent" and "halogen atom" in R ₁ "Alkyl which may have a substituent", "Alkoxy which may have a substituent", and "Aryloxy which may have a substituent" have the same meaning.

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

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

In A, examples of the alkylene group which may have a substituent include methylene, ethylene, n-propylene, n-butylene, n-hexyl, n-heptyl, n-octyl, and n-dodecyl. 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 a color filter of the present invention contains an azo pigment composed of a compound represented by the general formula (1) or the general formula (2). In the colorant for a color filter of the present invention, in order to adjust the chromaticity and the like, a pigment other than the compound represented by the general formula (1) or the general formula (2) may be used within a range that does not impair the effect of the present invention. Or dyes and other colorants. These pigments and dyes can be used alone or as a mixture of two or more kinds at 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: 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, Red pigments such as 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, or 287. Examples of the red dye include dibenzopyran dyes, azo (pyridone-based, barbituric acid-based) dyes, bisazo dyes, anthraquinone dyes, and methine dyes. In addition, it may be a lake pigment obtained by lake-forming these dyes, an inorganic salt of an acidic dye having an acidic group such as a sulfonic acid or a carboxylic acid, a salt-forming compound of an acidic dye and a nitrogen-containing compound, or an acidic dye. Forms of sulfonamide.

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 the following general formula (3) Yellow pigment. Examples of the orange dye and / or yellow dye include quinoline-based, azo-based (pyridone-based, barbituric acid-based, and metal complex-based), diazo-based, and methine-based. .

Among the preferred colorants used in combination, from the viewpoints of fastness such as heat resistance and light resistance and the chromaticity range, azo-based, naphtholazo-based, diketopyrrolopyrrole Based, anthraquinone based, quinophthalone based, and fluorene based pigments. Specific examples include CI Pigment Red 269, 177, 254, 242, CI Pigment Yellow 138, 139, 150, 185, a yellow pigment represented by the following general formula (3), and brominated diketopyrrolopyrrole Pyrrole pigment.

In particular, from the viewpoints of brightness and color strength, CI Pigment Red 254, 242, CI Pigment Yellow 138, 139, and 150, a yellow pigment represented by the following general formula (3), and bromide 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, alkyl ammonium salts, phthalimidoimine methyl groups which may have a substituent, or sulfamoniums which may have a substituent 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.

Here, examples of the halogen atom include fluorine, chlorine, bromine, and iodine.

Examples of the alkyl group which may have a substituent include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, third butyl, neopentyl, n-hexyl, n-octyl, Linear or branched alkyl groups such as stearyl, 2-ethylhexyl, and other examples include trichloromethyl, trifluoromethyl, 2,2,2-trifluoroethyl, 2,2-di Bromoethyl, 2,2,3,3-tetrafluoropropyl, 2-ethoxyethyl, 2-butoxyethyl, 2-nitropropyl, benzyl, 4-methylbenzyl, An alkyl group having a substituent, such as 4-tert-butylbenzyl, 4-methoxybenzyl, 4-nitrobenzyl, 2,4-dichlorobenzyl, and the like.

Examples of the alkoxy group which may have a substituent include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, an n-butoxy group, an isobutoxy group, a third butoxy group, and neopentyl. Straight or branched chain alkoxy groups such as oxy, 2,3-dimethyl-3-pentoxy, n-hexyloxy, n-octyloxy, stearyloxy, 2-ethylhexyloxy, etc. Can also be listed: trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropoxy, 2,2-di-trifluoro Alkoxy groups having a substituent such as methylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, and benzyloxy.

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

Examples of the acidic group include -SO ₃ H and -COOH. Examples of the monovalent to trivalent metal salt of the acidic group include sodium salt, potassium salt, magnesium salt, calcium salt, iron salt, Aluminum salts, etc. Examples of the alkylammonium salt of an acidic group include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, and stearylamine, palmityl trimethylammonium, and dilauryldimethyl Tertiary alkylammonium salts such as ammonium and distearyldimethylammonium salts.

Among the phthalimidoiminomethyl groups which may have a substituent (C ₆ H ₄ (CO) ₂ N-CH _2- ), and the aminesulfonyl groups (H ₂ NSO _2- ) which may have a substituent Examples of the "substituent" include the above-mentioned halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aryl group which may have a substituent.

Adjacent groups in Z ₁ to Z ₄ and / or Z ₁₀ to Z ₁₃ in the general formula (3) may be integrated to form an aromatic ring which may have a substituent. Examples of the aromatic ring include a hydrocarbon aromatic ring and a heteroaromatic ring. Examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of the heteroaromatic ring include 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.

Specific examples of the yellow pigment represented by the general formula (3) used in the colorant for a color filter of the present invention include the quinophthalone compound (a) to the quinophthalone compound (r) shown below. ), Etc., but the present invention is not limited to these. 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 in combination, a dye that exhibits red and purple colors and has any form of an oil-soluble dye, an acid dye, a direct dye, or a basic dye is preferable.

Among these, a dibenzopyran-based oil-soluble dye, a dibenzopyran-based basic dye, and a dibenzopyran-based acid dye are preferably used because of their excellent hue. In addition, it may be a lake pigment obtained by lake-forming these dyes, an inorganic salt of an acidic dye having an acidic group such as a sulfonic acid or a carboxylic acid, a salt-forming compound of an acidic dye and a nitrogen-containing compound, or an acidic dye. Forms of sulfonamide.

Examples of the 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, and 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 and the like. 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, and CI Solvent are more preferred as a rose red oil-soluble dye with high color rendering properties. Purple 2.

Examples of the dibenzopyran-based basic dyes include C.I. Basic Red 1 (Rose Red 6GCP), 8 (Rose Red G), C.I. Basic Violet 10 (Rose Red B), and the like. Among these, 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 (Red Algae Red (Edible Red No. 3)), CI Acid Red 52 (Acid Red Rose), CI Acid Red 87 (Eosin G (edible) Red No. 103)), CI Acid Red 92 (Acid Oleander 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, or rose red acid dye as dibenzopyran acid dyes. CI acid red 52 (acid rose red), CI acid red 289, acid rose red G, CI acid violet 9.

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

When the red pigment, yellow pigment, orange pigment, and dye are used in combination, the content of the compound represented by the general formula (1) or the general formula (2) is 10% by mass based on 100% by mass of the total amount of the colorant. It is 90% by mass, preferably 20% by mass to 80% by mass. When the content of the compound represented by the general formula (1) or the general formula (2) is 10% by mass or less, the effect of excellent brightness and coloring power cannot be sufficiently exhibited.

<Average primary particle size of pigment>

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

To the powder of the pigment, propylene glycol monomethyl ether acetate was added, and a small amount of Disperbyk-161 was added as a resin-based dispersant, and dispersed in an ultrasonic cleaner for 1 minute to prepare a sample for measurement. With respect to this sample, three photographs (three fields of view) of primary particles of 100 or more pigments can be taken with a transmission electron microscope ("JEM-1200EX" manufactured by Japan Electronics Co., Ltd.). The size of 100 primary particles was measured sequentially. Specifically, the short-axis diameter and the long-axis diameter of the primary particles of each pigment are measured in nm units, and the average of the short-axis diameter and the long-axis diameter is regarded as the primary particle diameter of the pigment. The distribution of a total of 300 particles is approximated by the central value of each 5 nm scale (for example, 8 nm in the case of more than 6 nm and less than 10 nm) as the particle size of these particles, and is calculated based on each particle size and number. The number average particle diameter was calculated.

<Miniaturization of colorants>

The pigment used in the present invention can be used in a finer form. The pigment containing the compound represented by the general formula (1) or the general formula (2) is also preferably used for miniaturization. The method of miniaturization is not particularly limited, and for example, any one of wet grinding, dry grinding, and dissolution can be used, and a kneader method as one of the wet grinding can be performed as exemplified in the present invention. Salt milling.

The primary particle diameter of the finely-refined pigment is preferably 20 nm or more in terms of good dispersion in the colorant carrier. In addition, in order to form a filter segment having a high contrast ratio, it is preferably 100 nm or less. A particularly preferred range is a range from 25 nm to 85 nm.

The so-called salt milling treatment refers to the following processing, that is, using a kneader, a ternary mixer, a two-roller mill, a three-roller mill, a ball mill, a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent, After kneading machines such as attritors and sand mills perform mechanical kneading while heating, water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water. The water-soluble inorganic salt system functions as a crushing aid, and uses a high hardness of the inorganic salt to crush the pigment during salt milling. By optimizing the conditions when the pigment is subjected to salt milling, a pigment having a very fine primary particle size, a narrow distribution range, and a steep particle size distribution can be obtained.

As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate, and the like can be used. In terms of price, sodium chloride (table salt) is preferably used. In terms of both processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 parts by mass to 2000 parts by mass with respect to 100 parts by mass of the colorant, and most preferably used in an amount of 300 parts by mass to 1,000 parts by mass.

The water-soluble organic solvent exhibits the function of moistening 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 used. However, since the temperature rises during salt milling, and the solvent easily evaporates, a high-boiling point solvent having a boiling point of 120 ° C. or higher is preferred in terms of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentoxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, two 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, and the like. The water-soluble organic solvent is preferably used in an amount of 5 to 1,000 parts by mass, and most preferably used in an amount of 50 to 500 parts by mass, with respect to 100 parts by mass of the colorant.

When the pigment is subjected to salt milling, a 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 further preferably a part of the resin soluble in the organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by mass based on 100 parts by mass of the colorant.

In addition, when the pigment is subjected to salt milling, 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 thereof include an organic pigment, anthraquinone, acridone, or triazine, in which a basic substituent, an acidic substituent, or phthalate which may have a substituent is introduced. A compound of iminomethyl. These can be used individually or in mixture of 2 or more types.

The use amount of these pigment derivatives is preferably 2 parts by mass to 30 parts by mass, and most preferably 5 parts by mass to 20 parts by mass with respect to 100 parts by mass of the colorant.

<Coloring composition for color filter>

The coloring composition for a color filter 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. In the case of using it in the form of an alkali-developing coloring resist material, it is preferable to use an alkali-soluble vinyl resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic group. In addition, in order to improve the light sensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond may be used.

In particular, an active energy ray-curable resin having an ethylenically unsaturated double bond in a side chain is used for an alkali-developing coloring resist material, and when an active energy ray is used to form a coating film, the resin is made by By performing three-dimensional crosslinking to fix the colorant, the heat resistance becomes good, and the colorant's discoloration (deterioration of the spectral characteristics) due to heat can be suppressed. In addition, the development step also has the effect of suppressing aggregation and precipitation of colorant components.

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

In order to disperse the colorant better, the weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 10,000 to 80,000. 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 for the photosensitive coloring composition for color filters, a carboxyl group which functions as a coloring agent adsorption group and an alkali-soluble group during development, and an affinity group for a colorant carrier and a solvent The balance between the functioning aliphatic group and aromatic group is important for the dispersibility, permeability, developability, and further durability of the colorant. It is preferable to use a resin having an acid value of 20 mgKOH / g to 300 mgKOH / g. If the acid value is less than 20 mgKOH / g, the solubility in the developer is poor, and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, a fine pattern cannot remain.

As for the binder resin, in terms of good film-forming properties and various resistances, it is preferably used in an amount of 20 parts by mass or more based on 100 parts by mass of the total mass of the colorant. As the concentration of the colorant is high, it can exhibit good properties. In terms of color characteristics, it is preferably used in an amount of 1,000 parts by mass or less.

Examples of the thermoplastic resin used in the binder resin include acrylic resin, butyraldehyde resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, and vinyl chloride- Vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber system Resin, cellulose, polyethylene (HDPE (High Density Polyethylene, high density polyethylene), LDPE (Low Density Polyethylene, low density polyethylene)), polybutadiene, and polyimide resin. Among these, an acrylic resin is preferably used.

Examples of the ethylene-based alkali-soluble resin obtained by copolymerizing an ethylenically unsaturated monomer containing an acidic group include resins having an acidic group such as a carboxyl group and a fluorenyl group.

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

Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins having an unsaturated ethylenic double bond introduced by the method (i) or (ii) shown below.

[Method (i)]

As the method (i), for example, there is a method in which an unsaturated ethylenic monomer having an epoxy group is copolymerized with one or more other monomers to obtain a copolymer, and a side of the obtained copolymer is obtained. The chain epoxy group is added to a carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenic double bond, and the generated hydroxyl group is reacted with a polybasic acid anhydride to introduce an unsaturated ethylenic double bond and a 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 can be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth) acrylate is preferred.

Examples of the unsaturated monobasic acid include (meth) acrylic acid, butenoic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl group of (meth) acrylic acid, alkoxy group, halo group, and nitro group. Monocarboxylic acids, such as cyano substituents, etc., 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, etc. These may be used alone or in combination of two types. the above. The number of carboxyl groups may be increased. If necessary, tricarboxylic anhydride such as trimellitic anhydride or tetracarboxylic dianhydride such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups. In addition, if tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the unsaturated ethylenic double bond can be further increased.

As a similar method to the method (i), for example, there is a method in which an unsaturated ethylenic monomer having a carboxyl group is copolymerized with one or more other monomers to obtain a copolymer, and the obtained copolymer is obtained. A part of the side chain carboxyl group is added to an unsaturated ethylenic monomer having an epoxy group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[Method (ii)]

As the method (ii), there is a method of using a unsaturated ethylenic monomer having a hydroxyl group and copolymerizing another unsaturated monobasic acid monomer or other monomer having a carboxyl group, thereby obtaining a copolymer, and obtaining the obtained copolymer. The copolymer has a side chain hydroxyl group that reacts with an isocyanate group of an 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- or (meth) acrylate, or 4-hydroxybutyl (meth) acrylate, glycidyl (meth) acrylate, or hydroxyalkyl (meth) acrylates such as cyclohexanedimethanol mono (meth) acrylate, these can be used alone or in combination. 2 More than that. In addition, a polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the hydroxyalkyl (meth) acrylate may be used, or (Poly) ester mono (meth) acrylate obtained by addition of (poly) γ-valerolactone, (poly) ε-caprolactone, and / or (poly) 12-hydroxystearic acid. From a viewpoint of suppressing a coating film foreign body, 2-hydroxyethyl (meth) acrylate or glycidyl (meth) acrylate is preferable.

Examples of the unsaturated ethylenic monomer having an isocyanate group include 2- (meth) acryloxyethyl isocyanate and 1,1-bis [(meth) acryloxy] ethyl isocyanate. Esters are not limited to these, and two or more kinds may be used in combination.

<Organic solvent>

The coloring composition of the present invention is based on the purpose of easily dispersing the colorant sufficiently and penetrating into the colorant carrier, and coating the substrate on a substrate such as a glass substrate with a dry film thickness of 0.2 to 5 μm to form a filter segment. May contain organic solvents. The organic solvent is selected in consideration of the solubility and further the safety of each component of the coloring composition in addition to the good 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-cyclohexene-1-one, 3,3 , 5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, acetic acid 3-methoxy-3-methylbutyl, 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, second butylbenzene, third 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 monobutyl ether, ethylene glycol monobutyl ether Ether, glycol monobutyl ether acetate, glycol monopropyl ether, glycol mono Hexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, Diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexyl Ketones, 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, glycerol triacetate, triacetate Propylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether Ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methyl cyclohexanol, n-pentyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, acetic acid Propyl esters, dibasic acid esters, etc. These solvents can be used singly or as a mixture of two or more kinds at any ratio as needed.

The solvent may be used in an amount of 100 parts by mass to 10,000 parts by mass, preferably 500 parts by mass to 5000 parts by mass, with respect to 100 parts by mass of the coloring agent in the coloring composition.

<Photopolymerizable monomer>

The photopolymerizable monomer that can be added to the coloring composition of the present invention includes a monomer or oligomer that generates a transparent resin by curing with ultraviolet rays or heat.

Examples of monomers and oligomers that generate a transparent resin 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 (methyl) Acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di (meth) acrylate, neopentyl glycol Diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecyl (meth) acrylate, ester acrylate, methylolation Various methacrylates such as (meth) acrylates, epoxy (meth) acrylates, acrylic urethanes, and methacrylates, (Meth) acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl (meth) acryl Amine, N-vinylformamide, acrylonitrile, and the like are not necessarily limited to these. These photopolymerizable compounds can be used individually by 1 type or in mixture of 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 in terms 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 type or an alkali-developing type photosensitive coloring composition, and the composition is hardened by ultraviolet irradiation, and a photolithography method A filter segment is formed.

As the photopolymerization initiator, 4-phenoxydichloroacetophenone, 4-tert-butyldichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) can be used. ) -2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinylpropane -1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone Or acetophenone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinylphenyl) -butane-1-one; benzoin, benzoin methyl ether, benzoin ether, benzoin Benzoin compounds such as isopropyl ether, or diacetophenone dimethyl ketal; benzophenone, benzophenethylbenzoic acid, methyl benzylbenzoate, 4-phenylbenzophenone, Hydroxybenzophenone, acrylated benzophenone, 4-benzylidene-4'-methyldiphenylsulfide, or 3,3 ', 4,4'-tetrakis (third butyl peroxide (Carbonyl) benzophenone-based compounds such as benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Ketones, or thioxanthone compounds such as 2,4-diethylthioxanthone; 2,4,6-trichloro Triazine, 2-phenyl-4,6-bis (trichloromethyl) himetriazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) himetriazine, 2 -(P-tolyl) -4,6-bis (trichloromethyl) mesatriazine, 2-sunfloweryl-4,6-bis (trichloromethyl) mesatriazine, 2,4-bis (trichloro) (Methyl) -6-styryl-triazine, 2- (naphthalen-1-yl) -4,6-bis (trichloromethyl) -triazine, 2- (4-methoxy-naphthalene-1 -Yl) -4,6-bis (trichloromethyl) mesatriazine, 2,4-trichloromethyl- (sunfloweryl) -6-triazine, or 2,4-trichloromethyl- (4 '-Methoxystyryl) -6-triazine and other triazine compounds; 1,2-octanedione, 1- [4- (phenylthio) -2- (O-benzylidene oxime) ], Or oxime ester compounds such as O- (ethenyl) -N- (1-phenyl-2- pendantoxy-2- (4'-methoxy-naphthyl) ethylene) hydroxylamine; Phosphine-based compounds such as bis (2,4,6-trimethylbenzylidene) phenylphosphine oxide, or 2,4,6-trimethylbenzylidenediphenylphosphine oxide; 9,10-phenanthrene Quinone compounds such as quinone, camphorquinone, and ethyl anthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. These photopolymerization initiators may be used individually by 1 type, and may mix and use 2 or more types by arbitrary ratios as needed.

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

<Sensitizer>

Furthermore, the coloring composition for color filters of this invention may contain a sensitizer.

Examples of the sensitizer include unsaturated ketones represented by chalcone derivatives or dibenzylideneacetone, 1,2-dione derivatives represented by benzophenone or camphorquinone, and benzoin. Derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone ( thioxanthone) derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxazolate derivatives, such as polymethine pigments, acridine derivatives, and azine derivatives , Thiazine derivative, oxazine derivative, indolinoline derivative, osmium derivative, osmium derivative, squarium derivative, porphyrin derivative, tetraphenylporphyrin derivative, triarylmethane derivative , Tetrabenzoporphyrin derivative, Tetrapyrazino-porphyrazine derivative, Phthalocyanine derivative, Tetraazaporphyrazine derivative, Tetraquinoxaline porphyrazine derivative, Naphthol cyanine derivative, Subphthalocyanine Derivatives, pyranium derivatives, thiananium derivatives, New Zealand eggplant tetraphyllin derivatives, Rotene derivatives, spiropyran derivatives, spiroxazine derivatives, thiospiropyran derivatives, metal aromatic hydrocarbon complexes, organic ruthenium complexes, Michelinone derivatives, and the like. These sensitizers can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

Furthermore, as specific examples, the "Color Handbook" (1986, Kodansha) by Ogawara Shinzo and others, the "Chemistry of Functional Pigments" (1981, CMC) by Ogawara Shinzo, and others Sensitizers described in "Special Functional Materials" (1986, CMC) by the author, but are not limited to these. In addition, it may contain a sensitizer that shows absorption of light in the ultraviolet to near-infrared region.

Among the above sensitizers, particularly preferred sensitizers include thioxanthone derivatives, Michelinone derivatives, and carbazole derivatives. Further 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 Methanone, 4,4'-bis (ethylmethylamino) benzophenone, N-ethylcarbazole, 3-benzyl-N-ethylcarbazole, 3,6-benzophenone Fluorenyl-N-ethylcarbazole and the like.

The content of the sensitizer is preferably 3 to 60 parts by mass based on 100 parts by mass of the photopolymerization initiator contained in the coloring composition, and more preferably 5 in terms of photohardenability and developability. Part by mass to 50 parts by mass.

<Polyfunctional thiol>

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

Examples of the polyfunctional thiol include hexanedithiol, decane dithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithiopropionate, Ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolethane Tris (3-mercaptobutyrate), trimethylolpropane tri (3-mercaptobutyrate), trimethylolpropane tri (3-mercaptopropionate), pentaerythritol tetrathioglycolate, pentaerythritol tetra Thiopropionate, pentaerythritol tetra (3-mercaptopropionate), dipentaerythritol hexa (3-mercaptopropionate), trimercaptopropionate tri (2-hydroxyethyl) isocyanurate, 1,4 -Dimethyl mercaptobenzene, 2,4,6-trimercapto-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-triazine, and the like. 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 from 0.05 to 100 parts by mass, and more preferably from 1.0 to 50.0 parts by mass based on 100 parts by mass of the colorant.

By using a polyfunctional thiol in an amount of 0.05 parts by mass or more, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such an improvement in development resistance cannot be obtained.

<Leveling agent>

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 a leveling agent, dimethylsiloxane having a polyether structure or a polyester structure on the main chain is preferred. Specific examples of the dimethylsiloxane having a polyether structure on the main chain include FZ-2122 manufactured by Dow Corning Toray, BYK-333 manufactured by BYK-Chemie, and the like. Specific examples of the dimethylsiloxane having a polyester structure on the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. A dimethylsiloxane having a polyether structure on the main chain and a dimethylsiloxane having a polyester structure on the main chain can also be used in combination. The content of the leveling agent is usually 100 parts by mass with respect to the total mass of the coloring composition, and preferably 0.003 to 1.0 part by mass.

As a particularly good leveling agent, it is a type 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 little solubility in water and is added to a coloring composition In this case, the surface tension reducing ability of the leveling agent is low. The leveling agent is further useful as a leveling agent with good wettability to the glass plate despite its low surface tension reducing ability. It can be preferably used in an amount where the coating film defects caused by foaming do not appear. Leveling agent that fully suppresses chargeability. As the leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyethylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit. 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 dimethyl polysiloxane may be a side chain type in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethyl polysiloxane, and the dimethyl polysiloxane is bonded to the dimethyl polysiloxane. Either a terminally modified type of the end of the base polysiloxane, or a linear block copolymer type which is repeatedly and repeatedly bonded to dimethyl polysiloxane. The 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.

To the leveling agent, an anionic, cationic, nonionic, or amphoteric surfactant may also be added auxiliaryly. The surfactant may be used by mixing two or more kinds. Examples of the anionic surfactant to be added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salt of styrene-acrylic acid copolymer, and alkyl group. 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, polyoxyethylene alkyl ether phosphate, etc. of acrylic copolymers.

Examples of the cationic surfactant to be added to the leveling agent include alkyl quaternary ammonium salts or ethylene oxide adducts thereof. Examples of non-ionic surfactants added to the leveling agent include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, Polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc. Examples of the amphoteric surfactants which are added to the leveling agent include alkyl betaines such as alkyldimethylaminoacetic acid betaine, and amphoteric surfactants such as alkylimidazoline.

<Ultraviolet absorbent, polymerization inhibitor>

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

Examples of the ultraviolet absorber include 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 2,6-bis (4-phenylphenyl) -1,3,5-triazine and other hydroxyphenyltriazines, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2H-benzotriazol-2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (3-thirdbutyl-5-methyl-2- (Hydroxyphenyl) benzotriazoles such as 5-chlorobenzotriazole, 2,4-dihydroxybenzophenone, 2-hydroxy-4-octyloxybenzophenone, 2,2 ', 4 2,4'-tetrahydroxybenzophenones and other benzophenones, salicylic acid phenyl esters, salicylic acid p-tert-butylphenyl esters and other salicylates, 2-cyano-3,3'- Cyanoacrylates such as diphenylethyl acrylate, 2,2,6,6-tetramethylpiperidine-1-oxy radical (triacetone-amine-N-oxy 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 hydrazine-2,4-diyl] [(2,2,6,6-tetramethyl-4-piperidinyl) imino]. These ultraviolet absorbers can be used individually by 1 type or in mixture of 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. Hydroquinone derivatives such as 4-methoxy-1-naphthol, tert-butylcatechol, and phenol compounds, phenothiazine, bis- (1-dimethylbenzyl) phenothiazine, Amine compounds such as 3,7-dioctylphenothiazine, copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, diphenyl Copper and manganese salt compounds such as manganese dithioaminoformate, 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxyamine, N-nitrosophenylhydroxyamine And other nitroso compounds and their ammonium or aluminum salts. 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 may be used in an amount of 0.01 to 20 parts by mass, and preferably 0.05 to 10 parts by mass based on 100 parts by mass of the coloring agent in the coloring composition.

By using an ultraviolet absorber or a polymerization inhibitor in an amount of 0.01 parts by mass or more, a better imaging degree can be obtained.

<Antioxidant>

The coloring composition for a color filter of the present invention may contain an antioxidant to increase the transmittance of the coating film. Antioxidants prevent the photopolymerization initiator contained in the coloring composition for color filters from yellowing due to oxidation by thermal steps during thermal hardening or ITO (Indium Tin Oxide) annealing, which can improve the coating film. Transmittance. Therefore, by including an antioxidant, yellowing due to oxidation during the heating step can be prevented, and a high transmittance of the coating film can be obtained.

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

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

Examples of hindered amine antioxidants include bis (2,2,6,6-tetramethyl-4-piperidinyl) sebacate, and 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) Propylamine, tetrakis (2,2,6,6-tetramethyl-4-piperidinyl) 1,2,3,4-butanetetracarboxylic acid, poly [{6- (1,1,3 , 3-tetramethylbutyl) imino-1,3,5-triazine-2,4-diyl} {(2,2,6,6-tetramethyl-4-piperidinyl) Amine} hexamethyl {(2,2,6,6-tetramethyl-4-piperidinyl) imino}], poly [(6-morpholinyl-1,3,5-triazine- 2,4-diyl) {(2,2,6,6-tetramethyl-4-piperidinyl) imino} hexamethylene {(2,2,6,6-tetramethyl-4 -Piperidinyl) imino}], 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 and the like.

Examples of the phosphorus-based antioxidant include tris [2-[[2,4,8,10-tetra (1,1-dimethylethyl) dibenzo [d, f] [1,3,2] Dioxaphosphoheptene-6-yl] oxy] ethyl] amine, tris [2-[(4,6,9,11-tetratert-butyldibenzo [d, f] [1 , 3,2] Dioxaphosphohepten-2-yl) oxy] ethyl] amine, ethylbis (2,4-di-tert-butyl-6-methylphenyl) phosphite .

Examples of the thioether-based antioxidant include 2,2-thio-diethylidenebis [3- (3,5-di-third-butyl-4-hydroxyphenyl) propionate], 2,4 -Bis [(octylthio) methyl] o-cresol, 2,4-bis [(laurylthio) methyl] o-cresol and the like.

The content of the antioxidant is preferably used in an amount of 0.1 to 5 parts by mass out of 100 parts by mass of the total solid components of the coloring composition for color filters. 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 significantly reduced.

<Other ingredients>

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

Examples of the silane coupling agent include vinyl silanes such as vinyltri (β-methoxyethoxy) silane, vinylethoxysilane, and vinyltrimethoxysilane, and γ-methacryloxy (Meth) acrylic silanes such as propyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethyl Oxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) methyltriethoxysilane, γ-glycidyloxy Epoxysilanes such as propyltrimethoxysilane, γ-glycidyloxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β ( Aminoethyl) γ-aminopropyltriethoxysilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxy Silanes, amines such as γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, etc. Thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane .

The silane coupling agent may 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 coloring agent in the coloring composition.

Examples of the amine-based compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, and 4-dimethylamine. Isoamylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N, N-dimethyl-p-toluidine and the like.

<Manufacturing method of coloring composition for color filters>

In the coloring composition for color filters of the present invention, a colorant can be used in a colorant carrier such as a resin and / or a solvent, and a kneader, a two-roll mill, a three-roll mill, a ball mill, Various dispersing means such as a horizontal sand mill, a vertical sand mill, a ring bead mill, or an attritor are finely dispersed and produced (colorant dispersion). In this case, two or more kinds of coloring agents may be dispersed in the colorant carrier at the same time, or the coloring agents each dispersed in the coloring material 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 subsequently adding it to the prepared colorant dispersion. When the solubility of a colorant such as a dye is high, specifically, if the solubility of the solvent used is high, and the solvent is dissolved by stirring, it is not necessary to disperse it to the fineness as described above, so that foreign matter is not recognized. Manufacturing.

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

<Dispersion aid>

When dispersing a colorant in a colorant carrier, it is preferred to contain not only a resin-based dispersant but also a dispersing aid such as a pigment derivative and a surfactant. The dispersing aid has a large effect of preventing the re-aggregation of the dispersing colorant. Therefore, the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersing aid has good brightness and storage stability.

<Resin-based dispersant>

The coloring composition for color filters of the present invention preferably further contains a resin-based dispersant having an acidic substituent.

The resin-based dispersant includes a colorant affinity site (having the property of being adsorbed on a colorant) and a site compatible with the colorant carrier, and exerts adsorption on the colorant to stabilize the dispersion of the colorant in the colorant carrier. The role. As the resin-based dispersant, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamines, polycarboxylic acids, polycarboxylic acid (partial) amine salts, and polycarboxylic acids can be used. Ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminophosphonium phosphates, hydroxyl-containing polycarboxylic acid esters, or modifications thereof, by poly (lower eneimine) Oily dispersants such as amidine or its salt formed by reaction with a polyester having a free carboxyl group, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylate copolymer, styrene -Water-soluble resins such as maleic acid copolymers, polyvinyl alcohol, polyvinyl pyrrolidone or water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide / propylene oxide These compounds can be used alone or in combination of two or more, but they are not necessarily limited to these.

Examples of 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, Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, manufactured by Japan's Lubrizol Corporation, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47 manufactured by BASF , 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., Ajisper manufactured by Ajinomoto Fine-Techno of (Ajinomoto Fine-Techno) Company PA111, PB711, PB821, PB822, PB824 and the like.

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

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

(S2) Resin-based dispersant 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 anhydride and / or a tetracarboxylic dianhydride. polymer.

[Resin-based dispersant (S1)]

The resin-based dispersant (S1) can be produced by a known method such as WO2008 / 007776, Japanese Patent Laid-Open No. 2008-029901, and Japanese Patent Laid-Open No. 2009-155406. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the terminal, and can be obtained, for example, in the form of a polymer which makes an ethylenically unsaturated monomer in the presence of the compound (q) having a hydroxyl group. (r) Polymerization. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since there are preferably a plurality of terminal hydroxyl groups, a compound (q1) having two hydroxyl groups and one thiol group in the molecule can be preferably used among them.

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

[Resin-based dispersant (S2)]

The resin-based dispersant (S2) can be produced by a known method such as Japanese Patent Laid-Open No. 2009-155406, Japanese Patent Laid-Open No. 2010-185934, and Japanese Patent Laid-Open No. 2011-157416. It is obtained by making an ethylenically unsaturated monomer (r) in the presence of a reaction product of a hydroxyl group of a compound (q) having a hydroxyl group with an acid anhydride group of a tricarboxylic anhydride and / or a tetracarboxylic dianhydride. ) Polymerize. Among them, a polymer formed by the following manner, that is, the hydroxyl group of the compound (q1) having two hydroxyl groups and one thiol group in the molecule, and tricarboxylic anhydride and / or tetracarboxylic acid di The ethylenically unsaturated monomer (r) containing the monomer (r1) is polymerized in the presence of the reaction product of the anhydride group of the anhydride.

The difference between (S1) and (S2) is in the introduction of the polymer site for polymerizing the ethylenically unsaturated monomer (r) first or later. Although molecular weight and the like may be slightly different depending on various conditions, as long as the raw materials and reaction conditions are the same, they are theoretically the same.

The resin-based 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 used in a range of about 5 parts by mass to about 100 parts by mass from the viewpoint of film forming properties.

<Pigment derivative>

The coloring composition for a color filter of the present invention preferably further contains a pigment derivative. Pigment derivatives may also be included in azo pigments.

As the pigment derivative used in the present invention, a known pigment derivative in which an organic pigment residue has an acidic group, a basic group, a neutral group, or the like can be used. Examples include compounds having acidic functional groups such as sulfo, carboxyl, and phosphate groups, and amine salts thereof, compounds having a sulfoamido group or basic functional groups such as tertiary amine groups at the ends, phenyl groups, or Compounds with neutral functional groups such as phthalimide alkyl groups. Examples of the organic pigment include phthalates such as diketopyrrolopyrrole-based pigments, copper phthalocyanine, zinc phthalocyanine, aluminum phthalocyanine, copper halogenated phthalocyanine, zinc halogenated phthalocyanine, aluminum halogenated phthalocyanine, and metal-free phthalocyanine. Cyan pigments, amino anthraquinone, diamino dianthraquinone, anthracene, anthraquinone, flavone, anthracene, indanthrene, dermatanthone, purple anthrone, and other anthraquinone pigments, quinacridone Pigments, dioxazine-based pigments, perinone-based pigments, fluorene-based pigments, thiazine indigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, indole-based pigments such as benzoisoindole, Isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, threne-based pigments, metal-complex-based pigments, azo, disazo, polyazo Azo-based pigments such as nitrogen.

More specific examples include: 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, WO2009 / 025325 Booklet, WO2009 / 081930 Booklet, Japanese Patent Laid-Open No. 2011-162662, WO2011 / Booklet 052617, Japanese Patent Laid-Open Publication No. 2012-172092, Japanese Patent Laid-Open Publication No. 2012-208329, Japanese Patent Laid-Open Publication No. 2012-226110, WO2012 / 102399 Brochure, Japanese Patent Laid-Open Publication No. 2014-5439, The well-known pigment derivatives described in WO2016 / 163351 pamphlet, Japanese Patent Laid-Open No. 2017-156397, Japanese Patent No. 5753266, etc. can be used alone or in combination of two or more. Moreover, in these documents, a pigment derivative may be described as a derivative, a pigment derivative, a pigment dispersant, or simply as a compound. The organic pigment residue has an acidic group, a basic group, and a neutral group. A functional compound such as a radical has the same meaning as a pigment derivative.

Among the pigment derivatives used in the present invention, a pigment derivative having a basic substituent is preferred because the effect of suppressing the aggregation of the pigments is significant. Further, as the organic pigment 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, and alkylnaphthalenesulfonic acid. Sodium, alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl triethanolamine, lauryl ammonium sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkane Anionic surfactants such as polyether phosphate; polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate, polyoxyethylene sorbitan monostearic acid Non-ionic surfactants such as esters, polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts or their ethylene oxide adducts; alkyldimethylaminoacetic acid Ampholytic surfactants such as alkyl betaines such as betaine and alkyl imidazolines; 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 from 0.1 to 55 parts by mass, and more preferably from 0.1 to 45 parts by mass, with respect to 100 parts by mass of the colorant. When the content of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the effect of addition. If 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 a centrifugal separation, a filtration using a sintering filter or a membrane filter, etc., to coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and more preferably 0.5 μm or more Remove coarse particles and mixed dust. As described above, the coloring composition preferably does not substantially contain particles of 0.5 μm or more. It is more preferably 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 provided with a red filter segment, a green filter segment, and a blue filter segment on a substrate, and may further include a magenta filter segment, The color filter of the cyan filter segment or the yellow filter segment, and the at least one filter segment is formed by the coloring composition of the present invention.

<Manufacturing Method of Color Filter>

The color filter of the present invention can be manufactured by a printing method or a photolithography method. When the filter segment is formed by the 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, printing of fine patterns with high dimensional accuracy and smoothness can be performed. In order to print, it is preferable to set it as the composition which does not dry and solidify ink, such as on a printing plate or a printing blanket. In addition, it is also important to control the fluidity of the ink on the printing press. It is also possible to adjust the viscosity of the ink using dispersants or extender pigments.

In the case of forming a filter segment by a photolithography method, the coloring composition prepared as the above-mentioned solvent-developed or alkali-developed coloring resist material is spray-coated or spin-coated, and slit-coated. Coating methods such as cloth and roll coating are applied on a transparent substrate so that the dry film thickness becomes 0.2 μm to 5 μm. The film which has been dried as necessary is subjected to ultraviolet exposure 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, the developer is immersed in a solvent or an alkali developing solution, or the developing solution is sprayed by spraying, etc., the uncured portion is removed to form a desired pattern, and then the same operation is repeated for other colors to produce a color filter. Furthermore, in order to accelerate the polymerization of the colored resist material, heating may be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

During the development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as the alkali developing solution, and an organic base such as dimethylbenzylamine or triethanolamine may also be used. A defoaming agent or a surfactant may be added to the developer.

In addition, in order to increase the sensitivity of ultraviolet exposure, the color resist material may be coated and dried, and then a water-soluble or alkali-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin may be coated and dried to prevent the formation of oxygen. After the resulting polymerization-inhibited film, ultraviolet exposure was performed.

In addition to the above method, the color filter of the present invention can also be manufactured by an electrodeposition method, a transfer method, an inkjet method, or the like. The coloring composition of the present invention can be used in any method. In addition, the electrodeposition method is a method of manufacturing a color filter by the following methods, that is, using a transparent conductive film formed on a substrate and electrophoresis of colloidal particles on the transparent conductive film to form each color The segments are filtered, thereby making a color filter. The transfer method is a method in which a filter segment is formed in advance on the surface of a releasable transfer substrate, and the filter segment is transferred 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 may 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 not limited. In addition, a thin film transistor (TFT; Thin Film Transistor) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment is formed. In addition, on the color filter of the present invention, an overcoat film, a transparent conductive film, or the like is formed as necessary.

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

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

The LCD panel can be used for color filters such as twisted nematic (TN), super twisted nematic (STN; Super Twisted Nematic), in-plane switching (IPS), vertical alignment (VA), and optically compensated bending (OCB). LCD display mode for colorization.

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

[Example]

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

<Weight average molecular weight (Mw) of the resin>

The weight-average molecular weight (Mw) of the resin is a GPC (Gel Permeation Chromatography; GPC) equipped with a TSKgel column (manufactured by Tosoh Corporation) using a RI (Refractive Index; refractive index) detector (Tosoh (Manufactured by the company, HLC-8120GPC), and a weight average molecular weight (Mw) in terms of polystyrene measured by using THF (Tetrahydrofuran; tetrahydrofuran) as a developing solvent.

<Identification method of azo pigment>

To identify the azo pigments of the present invention, a MALDI (Matrix Assisted Laser Desorptioh Ionization; matrix-assisted laser desorption free) mass spectrometry device manufactured by Bruker Daltonics was used. Spectrometry; time-of-flight mass spectrometry)), the molecular ion peak of the obtained mass spectrum is identified with the mass obtained by calculation, and further, 2400 CHN Element Analyser manufactured by PerkinElmer is used to obtain each element The ratio is consistent with the theoretical value for identification.

<Contrast ratio of coating film>

The light emitted from the backlight unit for a liquid crystal display is polarized by a polarizing plate, and reaches a polarizing plate through a dry coating film of a colored composition coated on a glass substrate. If the polarizing plate is parallel to the polarizing surface of the polarizing plate, the light passes through the polarizing plate, but when the polarizing surface is orthogonal, the light is blocked by the polarizing plate. However, if the polarized light passes through the dry coating film of the coloring composition when it passes through the dry coating film of the coloring composition, it will cause scattering due to pigment particles, etc., and cause a deviation in a part of the polarizing surface. When the polarizing plates are parallel, the amount of light transmitted through the polarizing plate When the polarizing plate is reduced, a part of the light passes through the polarizing plate. This transmitted light was measured as the brightness on the polarizing plate, and the ratio (contrast ratio) of the brightness when the polarizing plates were parallel to the brightness when the polarizing plates were orthogonal was calculated.

(Contrast ratio) = (Brightness when parallel) / (Brightness when orthogonal)

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. During the measurement, in order to block unnecessary light, a black mask with a 1 cm square hole was placed on the measurement portion.

First, a method for producing an acrylic resin solution, a resin-based dispersant solution, a colorant, a coloring composition, and a photosensitive coloring composition used in Examples, Manufacturing Examples, and Comparative Examples will be described.

<Manufacturing method of acrylic resin solution>

(Preparation of acrylic resin solution 1)

In a separable four-necked flask, 196 parts of cyclohexanone was added to a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube and a stirring device, and the temperature was raised to 80 ° C. After the nitrogen in the reaction container was replaced, From the dropping tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, and p-cumylphenol ethylene oxide modified acrylate were added dropwise over 2 hours. A mixture of 20.7 parts of "Aronix M110" manufactured by Toa Synthesis Co., Ltd. and 1.1 parts of 2,2'-azobisisobutyronitrile. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C for 20 minutes, measure the non-volatile content, and add methoxyacetate to the previously synthesized resin solution so that the non-volatile content becomes 20%. Propyl ester to prepare an acrylic resin solution 1. The weight average molecular weight (Mw) was 26,000.

(Preparation of acrylic resin solution 2)

207 parts of cyclohexanone was added to a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen introduction tube, a dropping tube and a stirring device, and the temperature was raised to 80 ° C. After the nitrogen in the reaction container was replaced, From the dropping tube, 20 parts of methacrylic acid, 20 parts of p-cumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthesis Corporation), 45 parts of methyl methacrylate, and A mixture of 8.5 parts of 2-hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile. After completion of 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, nitrogen was stopped, stirring was performed while injecting dry air for 1 hour, and then the mixture was cooled to room temperature, and then 2-methacrylic acid was added dropwise at 70 ° C for 3 hours. A mixture of 6.5 parts of ethyl methyl ester (Karenz MOI manufactured by Showa Denko Corporation), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone. After completion of the dropwise addition, the reaction was further 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 dry at 180 ° C for 20 minutes, measure the non-volatile content, and add cyclohexanone to the previously synthesized resin solution so that the non-volatile content becomes 20%. Prepare an acrylic resin solution 2. The weight average molecular weight (Mw) was 18,000.

<Manufacturing method of resin type dispersant solution>

(Preparation of resin-based dispersant solution 1)

To 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 and used. Replace with nitrogen. The reaction vessel was heated to 80 ° C., and a solution in which 0.1 parts of 2,2′-azobisisobutyronitrile was dissolved in 10 parts of 3-mercapto-1,2-propanediol was added and reacted for 10 hours. By measuring the solid content, a 95% reaction was confirmed. Add 20 parts of pyromellitic anhydride, 200.0 parts of methoxypropyl acetate, and 0.40 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as catalyst, and react at 120 ° C for 7 hour. According to the measurement of the acid value, it was confirmed that 98% or more of the acid anhydride was semi-esterified and the reaction was terminated, and a polyester dispersant having an acid value of 77 mgKOH / g and a number average molecular weight of 8,500 was obtained. To this polyester dispersant, methoxypropyl acetate was added so that the solid content in the solid content measurement was 40%, to obtain a resin-based dispersant solution 1 having an aromatic carboxyl group.

(Preparation of resin-based dispersant solution 2)

To 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 and used. Replace with nitrogen. The reaction vessel was heated to 80 ° C., and a solution in which 0.1 parts of 2,2′-azobisisobutyronitrile was dissolved in 10 parts of 3-mercapto-1,2-propanediol was added and reacted for 10 hours. By measuring the solid content, a 95% reaction was confirmed. Added 36 parts of trimellitic anhydride, 200.0 parts of methoxypropyl acetate, and 0.40 parts of 1,8-diazabicyclo- [5.4.0] -7-undecene as a catalyst, and reacted at 120 ° C for 7 hours . According to the measurement of the acid value, it was confirmed that 98% or more of the acid anhydride was semi-esterified and the reaction was terminated, and a polyester dispersant having an acid value of 109 mgKOH / g and a number average molecular weight of 8,500 was obtained. To this polyester dispersant, methoxypropyl acetate was added so that the solid content in the solid content measurement was 40%, to obtain a resin-based dispersant solution 2 having an aromatic carboxyl group.

(Preparation of resin-based 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 parts of dimethylbenzylamine, and methoxyacetate were added. 41.8 parts of propyl propyl were replaced with nitrogen. The reaction vessel was heated to 100 ° C and reacted for 7 hours. After the acid value was measured, it was confirmed that more than 98% of the anhydride was semi-esterified, and then 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 third butyl acrylate were added. , 10.0 parts of hydroxymethyl methacrylate, 2.0 parts of ethyl acrylate, and added 0.10 parts of 2,2'-azobisisobutyronitrile and 60.0 parts of methoxypropyl acetate, and reacted for 10 hours. According to the measurement of the solid content, it was confirmed that the polymerization proceeded at 95% and the reaction was completed. A polyester dispersant having an acid value of 43 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 solid content measurement was 40%, to obtain a resin-based dispersant solution 3 having an aromatic carboxyl group.

(Preparation of resin-based 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 parts of dimethylbenzylamine, and methoxyacetate were added. 41.8 parts of propyl propyl were replaced with nitrogen. The reaction vessel was heated to 100 ° C and reacted for 7 hours. After the acid value was measured, it was confirmed that more than 98% of the anhydride was semi-esterified, and then 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 third butyl acrylate were added. , 10.0 parts of (3-ethyloxetane-3-yl) methyl methacrylate, 2.0 parts of ethyl acrylate, and added 0.10 parts of 2,2'-azobisisobutyronitrile and methoxyacetate 60.0 parts of propyl ester, reacted for 10 hours. By measuring the solid content, it was confirmed that the polymerization proceeded at 95% and the reaction was terminated. 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 solid content measurement was 40%, to obtain a resin-based dispersant solution 4 having an aromatic carboxyl group.

<Method for producing pigment derivative>

The manufacturing method and structure of the pigment derivative used by this invention are shown below. The present invention is not limited to this.

(Manufacture of pigment derivative 1)

With reference to Synthesis Example 3 of Japanese Patent No. 5786665, the pigment derivative 1 represented by Formula 5 was produced.

Equation 5

(Manufacture of pigment derivative 2)

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

(Manufacture of pigment derivative 3)

With reference to Production Example 6 of Japanese Patent No. 4,986,061, the pigment derivative 3 represented by Formula 7 was produced.

Equation 7

(Manufacture of Pigment Derivative 4)

With reference to Example 1 of Japanese Patent No. 5316690, a pigment derivative 4 represented by 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 thionyl chloride was added dropwise over 25 minutes, and 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-nitrate was added dropwise to the solution at room temperature for 1 hour. After diisophthalic acid dichloride, reflux was performed for 4 hours to complete the reaction. While neutralizing with a 10% sodium carbonate aqueous solution, distilling away toluene, reslurry using a 3% NaOH aqueous solution, filtering, and drying to obtain 28.0 parts of a compound represented by Formula 9 below.

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 sulfide hydrate (containing 65% of sodium sulfide) was dissolved in 55 parts to this solution. The resulting solution was refluxed for 6 hours to obtain 20.0 parts of a basic compound represented by the following formula 10.

Disperse 20.0 parts of the base compound represented by the above formula 10 in 200 parts of water, add ice to adjust the temperature to 5 ° C, add 20.0 parts of a 35% hydrochloric acid aqueous solution, and stir for 1 hour, then add 3.60 parts of sodium nitrite to 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% acetic acid aqueous solution, 65.0 parts of a 25% sodium hydroxide aqueous 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-naphthymidine 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 diazonium salt aqueous solution at 5 ° C for 30 minutes, and a coupling reaction was performed. The pH at this time was 4.4. After stirring for 1 hour to confirm the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 35.8 parts of the pigment derivative 5 represented by Formula 11.

(Manufacture of pigment derivative 6)

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

Equation 12

<Method for Manufacturing Colorant>

(Base compound)

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

(Manufacture 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 thionyl chloride was added and stirred at room temperature for 1 hour to obtain Carboxamidine chloride solution. In addition, a solution prepared by mixing 1000 parts of N-methylpyrrolidone and 48 parts of 1,3-phenylenediamine was prepared in advance, and a carboxyphosphonium chloride solution was added dropwise to the solution over 30 minutes. At this time, the temperature of the reaction solution was kept at 10 ° C. or lower, and dropwise addition was performed. After completion of the dropwise addition, after stirring at room temperature for 2 hours, the precipitated reaction product was collected by filtration to obtain the target product. Furthermore, 196 parts (yield: 98.5%) of the coupler compound [C-1] was obtained by washing with 1000 parts of methanol and drying under reduced pressure.

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

In place of 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 the coupler compound [ C-1] Production The same operation was performed to produce a coupler compound [C-2] to a coupler compound [C-70].

<Manufacture of azo pigment>

[Example 1]

(Manufacture of Azo Pigment 1)

After 185 parts of the basic compound [B-1] was added to 1500 parts of N-methylpyrrolidone, 294 parts of 35% hydrochloric acid was added, and the mixture was cooled to a temperature of -2 ° C to 0 ° C. After adding 208 parts of a 25% sodium nitrite aqueous solution to this solution, the solution was kept at 0 ° C. to 5 ° C. and stirred for 30 minutes to prepare a diazonium solution. In addition, a coupler solution composed of 167 parts of a coupler compound [C-1], 316 parts of a 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 at pH 5.4 over 10 minutes. After the dropwise addition was completed, the mixture was stirred at room temperature for 30 minutes, and further stirred while maintaining the temperature at 80 ° C. The precipitated reaction product was filtered, washed with hot water, and dried to obtain 343 parts of azo. Pigment 1 (yield: 95.8%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, it was identified as azo pigment 1.

[Example 2]

(Manufacture of Azo Pigment 2)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1, and using 169 parts of the basic compound [B-2], the same operation as in the production of the azo pigment 1 was performed to obtain 337. Parts of azo pigment 2 (yield: 98.1%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, it was identified as azo pigment 2.

[Example 3]

(Manufacture of Azo Pigment 3)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1, and using 210 parts of the basic compound [B-3], the same operation as in the production of the azo pigment 1 was performed to obtain 371 Parts of azo pigment 3 (yield: 96.7%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, it was identified as azo pigment 3.

[Example 4]

(Manufacture of Azo Pigment 4)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1, and using 181 parts of the basic compound [B-4], the same operation as in the production of the azo pigment 1 was performed to obtain 340. Parts of azo pigment 4 (yield: 95.6%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, it was identified as azo pigment 4.

[Example 5]

(Manufacture of Azo Pigment 5)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1, and using 222 parts of the basic compound [B-5], the same operation as in the production of the azo pigment 1 was performed to obtain 384. Parts of azo pigment 5 (yield: 97.1%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, it was identified as azo pigment 5.

[Example 6]

(Manufacture of Azo Pigment 6)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1 and using 228 parts of the basic compound [B-6], the same operation as in the production of the azo pigment 1 was performed to obtain 393 Parts of azo pigment 6 (yield: 97.8%). Based on the mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 6.

[Example 7]

(Manufacture of Azo Pigment 7)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1 and using 124 parts of the basic compound [B-7], the same operation as in the production of the azo pigment 1 was performed to obtain 287 Parts of azo pigment 7 (yield: 96.2%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 7.

[Example 8]

(Manufacture of Azo Pigment 8)

Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1, and 128 parts of the base compound [B-8], the same operation as in the production of the azo pigment 1 was performed to obtain 296 Parts of azo pigment 8 (yield: 97.9%). Based on the mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 8.

[Example 9]

(Manufacture of Azo Pigment 9)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1, and using 156 parts of the basic compound [B-9], the same operation as in the production of the azo pigment 1 was performed to obtain 322 Parts of azo pigment 9 (yield: 97.7%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, it was identified as azo pigment 9.

[Example 10]

(Manufacture of Azo Pigment 10)

Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1, and 187 parts of the base compound [B-10], the same operation as in the production of the azo pigment 1 was performed to obtain 357 Parts of azo pigment 10 (yield: 98.9%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 10 was identified.

[Example 11]

(Manufacture of Azo Pigment 11)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1, and using 190 parts of the basic compound [B-11], the same operation as in the production of the azo pigment 1 was performed to obtain 352 Parts of azo pigment 11 (yield: 96.6%). The result of mass spectrometry and elemental analysis of TOF-MS identified the azo pigment 11.

[Example 12]

(Manufacture of Azo Pigment 12)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1 and using 240 parts of the basic compound [B-12], the same operation as in the production of the azo pigment 1 was performed to obtain 399 Parts of azo pigment 12 (yield: 96.4%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 12 was identified.

[Example 13]

(Manufacture of Azo Pigment 13)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1 and using 207 parts of the basic compound [B-13], the same operation as in the production of the azo pigment 1 was performed to obtain 373 Parts of azo pigment 13 (yield: 97.9%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 13 was identified.

[Example 14]

(Manufacture of Azo Pigment 14)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1 and using 241 parts of the basic compound [B-14], the same operation as in the production of the azo pigment 1 was performed to obtain 394 Parts of azo pigment 14 (yield: 95.0%). The TOF-MS mass spectrum analysis and elemental analysis identified the azo pigment 14.

[Example 15]

(Manufacture of Azo Pigment 15)

Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1, and 215 parts of the base compound [B-15], the same operation as in the production of the azo pigment 1 was performed to obtain 372 Parts of azo pigment 15 (yield: 95.8%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 15 was identified.

[Example 16]

(Manufacture of Azo Pigment 16)

Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 1, and 233 parts of the base compound [B-16], the same operation as in the production of the azo pigment 1 was performed to obtain 390 Parts of azo pigment 16 (yield: 96.0%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 16 was identified.

[Example 17]

(Manufacture of Azo Pigment 17)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1, and using 298 parts of the basic compound [B-17], the same operation as in the production of the azo pigment 1 was performed to obtain 455 Parts of azo pigment 17 (yield: 96.5%). The result of mass spectrometry and elemental analysis of TOF-MS identified the azo pigment 17.

[Example 18]

(Manufacture of Azo Pigment 18)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 1 and using 415 parts of the basic compound [B-18], the same operation as in the production of the azo pigment 1 was performed to obtain 567 Parts of azo pigment 18 (yield: 96.5%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 18 was identified.

[Example 19]

(Manufacture of Azo Pigment 19)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 1, and using 219 parts of the coupler compound [C-57], the same operation as in the production of the azo pigment 1 396 parts of the azo pigment 19 was obtained (yield: 96.4%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 19 was identified.

Azo Pigment 19

[Example 20]

(Manufacture of Azo Pigment 20)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 169 parts of the basic compound [B-2], the same operation as in the production of the azo pigment 19 was performed to obtain 390 Parts of azo pigment 20 (yield: 98.7%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 20 was identified.

[Example 21]

(Manufacture of Azo Pigment 21)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 210 parts of the basic compound [B-3], the same operation as in the production of the azo pigment 19 was performed to obtain 430 Parts of azo pigment 21 (yield: 98.7%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 21 was identified.

[Example 22]

(Manufacture of Azo Pigment 22)

Instead of using 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and using 181 parts of the base compound [B-4], the same operation as in the production of the azo pigment 19 was performed to obtain 397 Parts of azo pigment 22 (yield: 97.4%). The result of mass spectrometry and elemental analysis of TOF-MS identified the azo pigment 22.

[Example 23]

(Manufacture of Azo Pigment 23)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 222 parts of the basic compound [B-5], the same operation as in the production of the azo pigment 19 was performed to obtain 433 Parts of azo pigment 23 (yield: 96.7%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 23 was identified.

[Example 24]

(Manufacture of Azo Pigment 24)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 228 parts of the basic compound [B-6], the same operation as in the production of the azo pigment 19 was performed to obtain 435 Parts of azo pigment 24 (yield: 95.8%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 24 was identified.

[Example 25]

(Manufacture of Azo Pigment 25)

Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and 124 parts of the base compound [B-7], the same operation as in the production of the azo pigment 19 was performed, and 344 was obtained Parts of azo pigment 25 (yield: 98.0%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 25 was identified.

[Example 26]

(Manufacture of Azo Pigment 26)

Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and 128 parts of the base compound [B-8], the same operation as in the production of the azo pigment 19 was performed to obtain 337 Parts of azo pigment 26 (yield: 95.2%). The TOF-MS mass spectrum analysis and elemental analysis identified the azo pigment 26.

[Example 27]

(Manufacture of Azo Pigment 27)

Instead of using 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and using 156 parts of the base compound [B-9], the same operation as in the production of the azo pigment 19 was performed to obtain 373 Parts of azo pigment 27 (yield: 97.6%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 27 was identified.

[Example 28]

(Manufacture of Azo Pigment 28)

Instead of using 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and using 187 parts of the base compound [B-10], the same operation as in the production of the azo pigment 19 was performed to obtain 393 Parts of azo pigment 28 (yield: 95.1%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 28 was identified.

[Example 29]

(Manufacture of Azo Pigment 29)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 190 parts of the basic compound [B-11], the same operation as in the production of the azo pigment 19 was performed to obtain 405 Parts of azo pigment 29 (yield: 97.4%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 29 was identified.

[Example 30]

(Manufacture of Azo Pigment 30)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 240 parts of the basic compound [B-12], the same operation as in the production of the azo pigment 19 was performed to obtain 456 Parts of azo pigment 30 (yield: 97.8%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 30 was identified.

[Example 31]

(Manufacture of Azo Pigment 31)

Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and 207 parts of the base compound [B-13], the same operation as in the production of the azo pigment 19 was performed to obtain 424 Parts of azo pigment 31 (yield: 97.8%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 31 was identified.

[Example 32]

(Manufacture of Azo Pigment 32)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 241 parts of the basic compound [B-14], the same operation as in the production of the azo pigment 19 was performed to obtain 457 Parts of azo pigment 32 (yield: 97.8%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 32 was identified.

Azo Pigment 32

[Example 33]

(Manufacture of Azo Pigment 33)

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

[Example 34]

(Manufacture of Azo Pigment 34)

Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and 233 parts of the base compound [B-16], the same operation as in the production of the azo pigment 19 was performed to obtain 445 Parts of azo pigment 34 (yield: 97.0%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 34 was identified.

[Example 35]

(Manufacture of Azo Pigment 35)

Instead of 185 parts of the base compound [B-1] used in the production of the azo pigment 19 and 298 parts of the base compound [B-17], the same operation as in the production of the azo pigment 19 was performed to obtain 500 Parts of azo pigment 35 (yield: 95.7%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 35.

[Example 36]

(Manufacture of Azo Pigment 36)

Instead of using 185 parts of the basic compound [B-1] used in the production of the azo pigment 19 and using 415 parts of the basic compound [B-18], the same operation as in the production of the azo pigment 19 was performed to obtain 629 Parts of azo pigment 36 (yield: 98.4%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 36 was identified.

[Example 37]

(Manufacture of Azo Pigment 37)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 172 parts of the coupler compound [C-2], the same operation as in the production of the azo pigment 4 was performed. 352 parts of the azo pigment 37 was obtained (yield: 97.6%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 37.

[Example 38]

(Manufacture of Azo Pigment 38)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 172 parts of the coupler compound [C-3], the same operation as in the production of the azo pigment 4 was performed. 357 parts of the azo pigment 38 was obtained (yield: 98.9%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 38 was identified.

[Example 39]

(Manufacture of Azo Pigment 39)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 177 parts of the coupler compound [C-4], the same operation as in the production of the azo pigment 4 was performed. 354 parts of the azo pigment 39 was obtained (yield: 96.7%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 39 was identified.

Azo Pigment 39

[Example 40]

(Manufacture of Azo Pigment 40)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 177 parts of the coupler compound [C-5], the same operation as in the production of the azo pigment 4 was performed. 357 parts of the azo pigment 40 was obtained (yield: 97.6%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 40.

[Example 41]

(Manufacture of azo pigment 41)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 182 parts of the coupler compound [C-6], the same operation as in the production of the azo pigment 4 was performed. 355 parts of the azo pigment 41 was obtained (yield: 95.8%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 41 was identified.

[Example 42]

(Manufacture of Azo Pigment 42)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 193 parts of the coupler compound [C-7], the same operation as in the production of the azo pigment 4 was performed. 366 parts of the azo pigment 42 was obtained (yield: 95.9%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 42 was identified.

[Example 43]

(Manufacture of Azo Pigment 43)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 192 parts of the coupler compound [C-8], the same operation as in the production of the azo pigment 4 was performed, 369 parts of the azo pigment 43 was obtained (yield: 96.8%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 43 was identified.

[Example 44]

(Manufacture of Azo Pigment 44)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 197 parts of the coupler compound [C-9], the same operation as in the production of the azo pigment 4 was performed. 381 parts of the azo pigment 44 was obtained (yield: 98.7%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 44 was identified.

[Example 45]

(Manufacture of Azo Pigment 45)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 178 parts of the coupler compound [C-10], the same operation as in the production of the azo pigment 4 was performed. 356 parts of the azo pigment 45 was obtained (yield: 97.0%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 45 was identified.

[Example 46]

(Manufacture of Azo Pigment 46)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 178 parts of the coupler compound [C-11], the same operation as in the production of the azo pigment 4 was performed. 355 parts of the azo pigment 46 was obtained (yield: 97.0%). The result of mass spectrometry and elemental analysis of TOF-MS identified the azo pigment 46.

Azo Pigment 46

[Example 47]

(Manufacture of Azo Pigment 47)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 183 parts of the coupler compound [C-12], the same operation as in the production of the azo pigment 4 was performed. 362 parts of the azo pigment 47 was obtained (yield: 97.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 47.

[Example 48]

(Manufacture of Azo Pigment 48)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 198 parts of the coupler compound [C-13], the same operation as in the production of the azo pigment 4 was performed. 382 parts of the azo pigment 48 was obtained (yield: 98.9%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 48 was identified.

[Example 49]

(Manufacture of azo pigment 49)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 173 parts of the coupler compound [C-14], the same operation as in the production of the azo pigment 4 was performed. 355 parts of the azo pigment 49 was obtained (yield: 98.4%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 49 was identified.

[Example 50]

(Manufacture of Azo Pigment 50)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 179 parts of the coupler compound [C-15], the same operation as in the production of the azo pigment 4 was performed. 358 parts of the azo pigment 50 was obtained (yield: 97.6%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 50 was identified.

[Example 51]

(Manufacture of Azo Pigment 51)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 179 parts of the coupler compound [C-16], the same operation as in the production of the azo pigment 4 was performed. 350 parts of the azo pigment 51 was obtained (yield: 95.3%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 51 was identified.

[Example 52]

(Manufacture of Azo Pigment 52)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 176 parts of the coupler compound [C-17], the same operation as in the production of the azo pigment 4 was performed. 360 parts of the azo pigment 52 was obtained (yield: 98.7%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 52 was identified.

[Example 53]

(Manufacture of Azo Pigment 53)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 184 parts of the coupler compound [C-18], the same operation as in the production of the azo pigment 4 was performed. 367 parts of the azo pigment 53 was obtained (yield: 98.6%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 53.

Azo Pigment 53

[Example 54]

(Manufacture of Azo Pigment 54)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 183 parts of the coupler compound [C-19], the same operation as in the production of the azo pigment 4 was performed. 365 parts of the azo pigment 54 was obtained (yield: 98.2%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 54 was identified.

[Example 55]

(Manufacture of Azo Pigment 55)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 183 parts of the coupler compound [C-20], the same operation as in the production of the azo pigment 4 was performed. 353 parts of the azo pigment 55 was obtained (yield: 95.0%). Using the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 55 was identified.

[Example 56]

(Manufacture of Azo Pigment 56)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 183 parts of the coupler compound [C-21], the same operation as in the production of the azo pigment 4 was performed. 365 parts of the azo pigment 56 was obtained (yield: 98.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 56.

[Example 57]

(Manufacture of Azo Pigment 57)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 197 parts of the coupler compound [C-22], the same operation as in the production of the azo pigment 4 was performed 379 parts of azo pigment 57 was obtained (yield: 98.4%). The result of mass spectrometry analysis and elemental analysis of TOF-MS identified the azo pigment 57.

[Example 58]

(Manufacture of Azo Pigment 58)

Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and 180 parts of the coupler compound [C-23], the same operations as those for the production of the azo pigment 4 were performed. 352 parts of azo pigment 58 was obtained (yield: 95.6%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, it was identified as azo pigment 58.

[Example 59]

(Manufacture of Azo Pigment 59)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 196 parts of the coupler compound [C-24], the same operation as in the production of the azo pigment 4 was performed. 369 parts of the azo pigment 59 was obtained (yield: 95.9%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 59.

[Example 60]

(Manufacture of Azo Pigment 60)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 174 parts of the coupler compound [C-25], the same operation as in the production of the azo pigment 4 was performed. 353 parts of the azo pigment 60 was obtained (yield: 97.6%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 60.

Azo Pigment 60

[Example 61]

(Manufacture of azo pigment 61)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 214 parts of the coupler compound [C-26], the same operation as in the production of the azo pigment 4 was performed. 392 parts of the azo pigment 61 was obtained (yield: 96.0%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 61 was identified.

[Example 62]

(Manufacture of Azo Pigment 62)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 192 parts of the coupler compound [C-27], the same operation as in the production of the azo pigment 4 was performed. 362 parts of the azo pigment 62 was obtained (yield: 95.1%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 62 was identified.

[Example 63]

(Manufacture of Azo Pigment 63)

Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and 180 parts of the coupler compound [C-28], the same operations as those for the production of the azo pigment 4 were performed. 364 parts of the azo pigment 63 was obtained (yield: 98.8%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 63 was identified.

[Example 64]

(Manufacture of Azo Pigment 64)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 187 parts of the coupler compound [C-29], the same operation as in the production of the azo pigment 4 was performed. 366 parts of azo pigment 64 was obtained (yield: 97.5%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 64.

[Example 65]

(Manufacture of Azo Pigment 65)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 194 parts of the coupler compound [C-30], the same operation as in the production of the azo pigment 4 was performed. 366 parts of the azo pigment 65 was obtained (yield: 95.8%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 65.

[Example 66]

(Manufacture of Azo Pigment 66)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 196 parts of the coupler compound [C-31], the same operation as in the production of the azo pigment 4 was performed. 374 parts of the azo pigment 66 was obtained (yield: 97.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 66.

[Example 67]

(Manufacture of Azo Pigment 67)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 190 parts of the coupler compound [C-32], the same operations as those for the production of the azo pigment 4 were performed. 368 parts of the azo pigment 67 was obtained (yield: 97.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 67.

Azo Pigment 67

[Example 68]

(Manufacture of Azo Pigment 68)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 186 parts of the coupler compound [C-33], the same operation as in the production of the azo pigment 4 was performed. 360 parts of the azo pigment 68 was obtained (yield: 96.4%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 68.

[Example 69]

(Manufacture of Azo Pigment 69)

Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and 186 parts of the coupler compound [C-34], the same operations as those for the production of the azo pigment 4 were performed, 359 parts of the azo pigment 69 was obtained (yield: 95.9%). Based on the mass spectrometry and elemental analysis of TOF-MS, the azo pigment 69 was identified.

[Example 70]

(Manufacture of Azo Pigment 70)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 212 parts of the coupler compound [C-35], the same operation as in the production of the azo pigment 4 was performed. 393 parts of the azo pigment 70 was obtained (yield: 98.2%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 70.

[Example 71]

(Manufacture of Azo Pigment 71)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 178 parts of the coupler compound [C-36], the same operation as in the production of the azo pigment 4 was performed. 352 parts of the azo pigment 71 was obtained (yield: 95.9%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 71 was identified.

[Example 72]

(Manufacture of Azo Pigment 72)

Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and 189 parts of the coupler compound [C-37], the same operations as those in the production of the azo pigment 4 were performed, 373 parts of the azo pigment 72 was obtained (yield: 98.8%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 72 was identified.

[Example 73]

(Manufacture of Azo Pigment 73)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 205 parts of the coupler compound [C-38], the same operation as in the production of the azo pigment 4 was performed. 376 parts of azo pigment 73 was obtained (yield: 95.6%). The result of mass spectrometry and elemental analysis of TOF-MS identified the azo pigment 73.

[Example 74]

(Manufacture of Azo Pigment 74)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 178 parts of the coupler compound [C-39], the same operation as in the production of the azo pigment 4 was performed. 358 parts of the azo pigment 74 was obtained (yield: 97.8%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 74.

Azo Pigment 74

[Example 75]

(Manufacture of Azo Pigment 75)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 218 parts of the coupler compound [C-40], the same operation as in the production of the azo pigment 4 was performed. 401 parts of the azo pigment 75 was obtained (yield: 98.8%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 75.

[Example 76]

(Manufacture of Azo Pigment 76)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 183 parts of the coupler compound [C-41], the same operation as in the production of the azo pigment 4 was performed. 367 parts of azo pigment 76 was obtained (yield: 98.7%). The TOF-MS mass spectrum analysis and elemental analysis identified the azo pigment 76.

[Example 77]

(Manufacture of Azo Pigment 77)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 185 parts of the coupler compound [C-42], the same operation as in the production of the azo pigment 4 was performed. 356 parts of azo pigment 77 was obtained (yield: 95.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 77.

[Example 78]

(Manufacture of Azo Pigment 78)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 191 parts of the coupler compound [C-43], the same operation as in the production of the azo pigment 4 was performed. 372 parts of azo pigment 78 was obtained (yield: 98.0%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 78.

[Example 79]

(Manufacture of Azo Pigment 79)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 211 parts of the coupler compound [C-44], the same operation as in the production of the azo pigment 4 was performed, 388 parts of the azo pigment 79 was obtained (yield: 97.2%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 79.

[Example 80]

(Manufacture of Azo Pigment 80)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and using 172 parts of the coupler compound [C-2], the same operation as in the production of the azo pigment 7 was performed. 301 parts of azo pigment 80 was obtained (yield: 98.9%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 80.

[Example 81]

(Manufacture of Azo Pigment 81)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and using 172 parts of the coupler compound [C-3], the same operation as in the production of the azo pigment 7 was performed. 298 parts of the azo pigment 81 was obtained (yield: 98.0%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 81 was identified.

[Example 82]

(Manufacture of Azo Pigment 82)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and using 192 parts of the coupler compound [C-8], the same operation as in the production of the azo pigment 7 was performed. 317 parts of azo pigment 82 was obtained (yield: 98.0%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 82 was identified.

[Example 83]

(Manufacture of Azo Pigment 83)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7 and using 178 parts of the coupler compound [C-11], the same operation as in the production of the azo pigment 7 was performed. 300 parts of azo pigment 83 was obtained (yield: 96.8%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 83 was identified.

[Example 84]

(Manufacture of Azo Pigment 84)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and using 180 parts of the coupler compound [C-23], the same operation as in the manufacture of the azo pigment 7 was performed. 307 parts of the azo pigment 84 was obtained (yield: 98.6%). As a result of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 84 was identified.

[Example 85]

(Manufacture of Azo Pigment 85)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7 and using 185 parts of the coupler compound [C-42], the same operation as in the production of the azo pigment 7 was performed. 309 parts of azo pigment 85 was obtained (yield: 98.6%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 85.

Azo Pigment 85

[Example 86]

(Manufacture of Azo Pigment 86)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and using 191 parts of the coupler compound [C-43], the same operation as in the production of the azo pigment 7 was performed. 317 parts of the azo pigment 86 was obtained (yield: 98.4%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 86.

[Example 87]

(Manufacture of Azo Pigment 87)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 195 parts of the coupler compound [C-45], the same operation as in the production of the azo pigment 7 was performed. 375 parts of azo pigment 87 was obtained (yield: 97.7%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 87 was identified.

Azo Pigment 87

[Example 88]

(Manufacture of Azo Pigment 88)

Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and 200 parts of the coupler compound [C-46], the same operations as those for the production of the azo pigment 4 were performed. 373 parts of azo pigment 88 was obtained (yield: 96.0%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 88.

[Example 89]

(Manufacture of Azo Pigment 89)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 211 parts of the coupler compound [C-47], the same operation as in the production of the azo pigment 4 was performed. 388 parts of azo pigment 89 was obtained (yield: 97.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 89.

[Example 90]

(Manufacture of Azo Pigment 90)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 251 parts of the coupler compound [C-48], the same operation as in the production of the azo pigment 4 was performed. 422 parts of the azo pigment 90 was obtained (yield: 96.1%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 90.

[Example 91]

(Manufacture of azo pigment 91)

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

[Example 92]

(Manufacture of Azo Pigment 92)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 263 parts of the coupler compound [C-50], the same operation as in the production of the azo pigment 4 was performed. 437 parts of the azo pigment 92 was obtained (yield: 96.9%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 92.

[Example 93]

(Manufacture of Azo Pigment 93)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 223 parts of the coupler compound [C-51], the same operation as in the production of the azo pigment 4 was performed. 396 parts of azo pigment 93 was obtained (yield: 96.2%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 93.

[Example 94]

(Manufacture of Azo Pigment 94)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 229 parts of the coupler compound [C-52], the same operation as in the production of the azo pigment 4 was performed. 409 parts of the azo pigment 94 was obtained (yield: 97.9%). As a result of mass spectrometry and elemental analysis by TOF-MS, the azo pigment 94 was identified.

[Example 95]

(Manufacture of Azo Pigment 95)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 244 parts of the coupler compound [C-53], the same operation as in the production of the azo pigment 4 was performed. 417 parts of the azo pigment 95 was obtained (yield: 96.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 95.

[Example 96]

(Manufacture of Azo Pigment 96)

Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and 201 parts of the coupler compound [C-54], the same operation as in the production of the azo pigment 4 was performed, 382 parts of the azo pigment 96 was obtained (yield: 98.1%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 96.

Azo Pigment 96

[Example 97]

(Manufacture of Azo Pigment 97)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 207 parts of the coupler compound [C-55], the same operation as in the production of the azo pigment 4 was performed 383 parts of the azo pigment 97 was obtained (yield: 96.9%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 97.

[Example 98]

(Manufacture of Azo Pigment 98)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 206 parts of the coupler compound [C-56], the same operation as in the production of the azo pigment 4 was performed. 383 parts of the azo pigment 98 were obtained (yield: 97.3%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 98.

[Example 99]

(Manufacture of Azo Pigment 99)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 229 parts of the coupler compound [C-58], the same operation as in the production of the azo pigment 4 was performed. 411 parts of the azo pigment 99 was obtained (yield: 98.4%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 99.

[Example 100]

(Manufacture of Azo Pigment 100)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 229 parts of the coupler compound [C-59], the same operation as in the production of the azo pigment 4 was performed, 400 parts of the azo pigment 100 was obtained (yield: 95.8%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 100.

[Example 101]

(Manufacture of Azo Pigment 101)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 270 parts of the coupler compound [C-60], the same operation as in the production of the azo pigment 4 was performed. 441 parts of the azo pigment 101 was obtained (yield: 96.4%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 101.

[Example 102]

(Manufacture of Azo Pigment 102)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 245 parts of the coupler compound [C-61], the same operation as in the manufacture of the azo pigment 4 was performed. 421 parts of the azo pigment 102 was obtained (yield: 97.3%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 102 was identified.

[Example 103]

(Manufacture of Azo Pigment 103)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 232 parts of the coupler compound [C-62], the same operation as in the production of the azo pigment 4 was performed, 405 parts of the azo pigment 103 was obtained (yield: 96.3%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 103 was identified.

Azo Pigment 103

[Example 104]

(Manufacture of Azo Pigment 104)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 231 parts of the coupler compound [C-63], the same operation as in the production of the azo pigment 4 was performed. 399 parts of the azo pigment 104 was obtained (yield: 96.3%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 104 was identified.

[Example 105]

(Manufacture of Azo Pigment 105)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 241 parts of the coupler compound [C-64], the same operation as in the production of the azo pigment 4 was performed. 423 parts of the azo pigment 105 was obtained (yield: 98.4%). Based on the results of mass spectrometry and elemental analysis by TOF-MS, the azo pigment 105 was identified.

[Example 106]

(Manufacture of Azo Pigment 106)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 281 parts of the coupler compound [C-65], the same operation as in the production of the azo pigment 4 was performed. 456 parts of the azo pigment 106 was obtained (yield: 97.1%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 106.

[Example 107]

(Manufacture of azo pigment 107)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 212 parts of the coupler compound [C-66], the same operation as in the production of the azo pigment 4 was performed. 395 parts of the azo pigment 107 was obtained (yield: 98.7%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 107 was identified.

[Example 108]

(Manufacture of Azo Pigment 108)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4 and using 211 parts of the coupler compound [C-67], the same operation as in the production of the azo pigment 4 was performed. 390 parts of azo pigment 108 was obtained (yield: 97.7%). Using the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 108 was identified.

Azo Pigment 108

[Example 109]

(Manufacture of Azo Pigment 109)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 225 parts of the coupler compound [C-68], the same operation as in the production of the azo pigment 4 was performed. 400 parts of the azo pigment 109 was obtained (yield: 96.9%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 109.

[Example 110]

(Manufacture of Azo Pigment 110)

Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and 230 parts of the coupler compound [C-69], the same operation as in the production of the azo pigment 4 was performed, 407 parts of the azo pigment 110 was obtained (yield: 97.4%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 110 was identified.

[Example 111]

(Manufacture of Azo Pigment 111)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 4, and using 237 parts of the coupler compound [C-70], the same operation as in the production of the azo pigment 4 was performed. 409 parts of the azo pigment 111 was obtained (yield: 96.0%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 111.

Azo Pigment 111

[Example 112]

(Manufacture of Azo Pigment 112)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7 and using 200 parts of the coupler compound [C-46], the same operation as in the production of the azo pigment 7 was performed. 320 parts of the azo pigment 112 was obtained (yield: 96.4%). Based on the results of mass spectrometry and elemental analysis of TOF-MS, the azo pigment 112 was identified.

[Example 113]

(Manufacture of Azo Pigment 113)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7 and using 211 parts of the coupler compound [C-47], the same operation as in the production of the azo pigment 7 was performed. 329 parts of the azo pigment 113 was obtained (yield: 96.0%). Based on the mass spectrum analysis and elemental analysis of TOF-MS, the azo pigment 113 was identified.

[Example 114]

(Manufacture of Azo Pigment 114)

Instead of using 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and using 251 parts of the coupler compound [C-48], the same operation as in the production of the azo pigment 7 was performed. 374 parts of the azo pigment 114 was obtained (yield: 97.6%). Based on the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 114 was identified.

[Example 115]

(Manufacture of Azo Pigment 115)

Instead of 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and 201 parts of the coupler compound [C-54], the same operation as in the production of the azo pigment 7 was performed. 319 parts of the azo pigment 115 was obtained (yield: 95.7%). According to the mass spectrometric analysis and elemental analysis of TOF-MS, the azo pigment 115 was identified.

[Example 116]

(Manufacture of Azo Pigment 116)

Except replacing 167 parts of the coupler compound [C-1] used in the production of the azo pigment 7, and using 206 parts of the coupler compound [C-56], the same operation as in the production of the azo pigment 7 was performed. 330 parts of azo pigment 116 was obtained (yield: 97.7%). The result of mass spectrometry and elemental analysis of TOF-MS identified azo pigment 116.

[Example 117]

(Production of azo pigment 117) Refinement 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 stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60 ° C. for 6 hours to perform a salt milling treatment. The obtained kneaded product was poured into 3 liters of warm water and stirred for 1 hour while heating to 70 ° C to prepare a slurry. After repeated filtration, washing with water to remove sodium chloride and diethylene glycol, the mixture was heated at 80 ° C. Drying all day and night, 78 parts of azo pigment 117 was obtained.

[Example 118]

(Production of azo pigment 118) Refinement step of azo pigment 22

80 parts of azo pigment 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.) and kneaded at 60 ° C. for 6 hours to perform a salt milling treatment. The obtained kneaded product was poured into 3 liters of warm water and stirred for 1 hour while heating to 70 ° C to prepare a slurry. After repeated filtration, washing with water to remove sodium chloride and diethylene glycol, the mixture was heated at 80 ° C. Drying all day and night, 78 parts of azo pigment 118 was obtained.

[Examples 119 to 124]

(Manufacture of azo pigment 120 to azo pigment 125)

In the production of the azo pigment 117, the azo pigment 4 and the pigment derivative were changed to the types and ratios shown in Table 4-2 in place of the azo pigment 4, and otherwise, the same method as the azo pigment 117 was used. Azo pigments 120 to 125 were obtained.

[Examples 125 to 130]

(Manufacture of azo pigments 126 to 131)

In the production of the azo pigment 118, the azo pigment 22 and the pigment derivative were changed to the types and ratios shown in Table 4-2 in place of the azo pigment 22, and the method was the same as that of the azo pigment 118. Azo pigments 126 to 131 were obtained.

[Manufacturing 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), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were added to a stainless steel 1-gallon kneader (Inoue Manufacturing Co., Ltd. (Manufactured by the 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 and stirred for 1 hour while heating to 70 ° C to prepare a slurry. After repeated filtration, washing with water to remove sodium chloride and diethylene glycol, the mixture was heated at 80 ° C. Drying all day and night, 98 parts of red colorant 1 (RCP-1) was obtained. The average primary particle diameter was 33 nm.

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

CI Pigment Red 254 ("Irgazin Red D3656 HD" manufactured by BASF) was changed to CI Pigment Red 177 (PR177) ("Cinilex Red SR3C" manufactured by CINIC), in addition to the manufacture of red colorant 1 Similarly, 97 parts of red colorant 2 (RCP-2) was obtained. The average primary particle diameter was 37 nm.

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

CI Pigment Red 254 ("Irgazin Red D3656 HD" manufactured by BASF) was changed to CI Pigment Red 242 (PR242) ("Sandorin Scarlet 4RF" manufactured by Clariant), in addition to the manufacture of red colorant 1 Similarly, 98 parts of red colorant 3 (RCP-3) was obtained. The average primary particle diameter was 39 nm.

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

CI Pigment Red 254 ("Irgazin Red D3656 HD" manufactured by BASF) was changed to CI Pigment Red 269 (PR269) ("Permanent Carmine 3810" manufactured by Sanyo Pigment Co., Ltd.). Production of 1 was performed in the same manner, and 98 parts of red colorant 4 (RCP-4) was obtained. The average primary particle diameter was 35 nm.

(Production 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, 200 parts of third pentanol dehydrated by molecular sieve and 140 parts of sodium third pentyl alkoxide were added, and heated 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, and the mixture was heated to 90 ° C. while being stirred to dissolve it to prepare a solution of the mixture. The heated solution of this mixture was vigorously stirred and slowly added dropwise to the above-mentioned alcoholate solution heated at 100 ° C at a fixed rate for 2 hours. After the dropwise addition was completed, 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 cover, and it cooled to -10 degreeC. The cooled mixture was rotated at a speed of 4000 rpm using a high-speed agitating disperser, while a small amount of the diketopyrrolopyrrole-based compound obtained by cooling to 75 ° C was added to the mixture one by one. Metal salt solution. At this time, while cooling the mixture of methanol, acetic acid, and water at a temperature of -5 ° C or lower, the addition rate of the alkali metal salt of the diketopyrrolopyrrole-based compound at 75 ° C was adjusted. On the one hand, it is added in small amounts one by one for about 120 minutes. When an alkali metal salt is added, red crystals are precipitated to form a red suspension. Then, the obtained red suspension was washed with an ultrafiltration device at 5 ° C, and then filtered and separated to obtain a red paste. This paste was re-dispersed in 3500 parts of methanol cooled to 0 ° C to prepare a suspension having a methanol concentration of about 90%. The suspension was stirred at 5 ° C for 3 hours, and granulation and washing with crystal transfer were performed. Then, it was separated by filtration using an ultrafiltration machine, and the obtained water paste of diketopyrrolopyrrole-based compound was dried at 80 ° C. for 24 hours and pulverized to obtain a brominated dibromide represented by formula (4). 150.8 parts of ketopyrrolopyrrole pigment.

100 parts of the 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) , And kneaded at 60 ° C for 6 hours, and then carried out salt milling treatment. The obtained kneaded product was poured into 3 liters of warm water and stirred for 1 hour while heating to 70 ° C to prepare a slurry. After repeated filtration, washing with water to remove sodium chloride and diethylene glycol, the temperature was 80 ° C. Drying all day and night, 98 parts of red colorant 5 (RCP-5) was obtained. The average primary particle diameter was 45 nm.

(Production 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 being heated to 70 ° C. to prepare a slurry, and filtered and washed repeatedly to remove sodium chloride and diethylene glycol at 80 ° C. Drying all day and night, 490 parts of yellow colorant 1 (YCP-1) was obtained. The average primary particle diameter was 63 nm.

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

500 parts of isoindoline 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 Seisakusho Manufactured by the company), 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 being heated to 70 ° C. to prepare a slurry, and filtered and washed repeatedly to remove sodium chloride and diethylene glycol at 80 ° C. Drying all day and night, 510 parts of yellow colorant 2 (YCP-2) was obtained. The average primary particle diameter was 68 nm.

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

500 parts of azo yellow pigment CI Pigment Yellow 150 ("Hostaperm Yellow HN4G" manufactured by Clariant), 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 knead at 120 ° C for 8 hours. Next, the kneaded product was poured into 5 liters of warm water, stirred for 1 hour while being heated to 70 ° C. to prepare a slurry, and filtered and washed repeatedly to remove sodium chloride and diethylene glycol at 80 ° C. Drying all day and night, 500 parts of yellow colorant 3 (YCP-3) was obtained. The average primary particle diameter was 60 nm.

(Production of yellow colorant 4 (YCP-4): quinophthalone compound (b))

To 200 parts of methyl benzoate, 40 parts of 8-aminoquinalidine, 150 parts of 2,3-naphthalenedicarboxylic acid anhydride, and 154 parts of benzoic acid were added, and the mixture was heated to 180 ° C. and stirred for 4 hours. After cooling to room temperature, the reaction mixture was poured 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 a quinophthalone compound (c). As a result of mass spectrometry of TOF-MS, it was identified as a 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, heated to 180 ° C, and reacted for 4 hours. By TOF-MS, the production of the quinophthalone compound (b) and the disappearance of the raw material compound (c-2) were confirmed. After cooling to room temperature, the reaction mixture was poured 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 a quinophthalone compound (b). As a result of mass spectrometry of TOF-MS, it was identified as a 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 1-gallon kneader (manufactured by Inoue Seisakusho) made of stainless steel, 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 being heated to 70 ° C. to prepare a slurry, and filtered and washed repeatedly to remove sodium chloride and diethylene glycol at 80 ° C. Drying all day and night, 480 parts of yellow colorant 4 (YCP-4) was obtained. The average primary particle diameter was 62 nm.

(Production of Green Colorant 1: PG58)

200 parts of phthalocyanine green pigment CI Pigment Green 58 ("FASTOGEN GREEN A110" manufactured by DIC Corporation), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were added to a stainless steel 1 gallon kneader (Inoue Manufacturing Co., Ltd. (Manufactured), kneaded for 6 hours at 80 ° C. Next, the kneaded product was poured into 8000 parts of warm water, and stirred while heating to 80 ° C. for 2 hours to prepare a slurry. The mixture was filtered and washed repeatedly to remove sodium chloride. After diethylene glycol and diethylene glycol were dried at 85 ° C for one day and night, 190 parts of green colorant 1 was obtained. The average primary particle diameter was 69 nm.

(Production of blue colorant 1: PB15: 6)

200 parts of phthalocyanine 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 stainless steel 1 gallon kneader (Manufactured by Inoue Seisakusho), and kneaded at 80 ° C for 6 hours. Next, the kneaded product was poured into 8000 parts of warm water, and heated to 80 ° C while stirring for 2 hours to make a slurry. After repeated filtration, washing with water to remove sodium chloride and diethylene glycol, the temperature was at 85 ° C. Drying all day and night, 190 parts of blue colorant 1 was obtained. The average primary particle diameter was 74 nm.

(Production of purple colorant 1: PV23)

200 parts of dioxazine purple pigment CI Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyocolor Co., Ltd.), 1400 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 8000 parts of warm water, and heated to 80 ° C while stirring for 2 hours to make a slurry. After repeated filtration, washing with water to remove sodium chloride and diethylene glycol, the temperature was 85 ° C Drying all day and night, 190 parts of purple colorant 1 was obtained. The average primary particle diameter was 69 nm.

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

<Manufacturing method of coloring composition>

[Example 201]

(Production of coloring composition (RM-1))

The following mixture was stirred and mixed in a uniform manner, and then dispersed using a zirconia bead with a diameter of 0.5 mm using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours. It was filtered with a filter having a pore size of 5.0 μm to produce a colored 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" (by 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, the coloring compositions (RM-2 to 131) were prepared in the same manner as the coloring composition (RM-1) except that the compositions shown in Tables 5 and 5-2 were changed.

[Example 331]

(Production of colored composition (RM-132))

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 A μm filter was used to produce a colored composition (RM-132) with a non-volatile content of 20% by 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): 8.3 parts

[Example 332]

(Production of colored composition (RM-133))

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 Filtered by a μm filter to produce a colored composition (RM-133) with a non-volatile content of 20% by 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-based dispersant solution ("Disperbyk-2000" (by solid content 40%) manufactured by BYK-Chemie): 10.4 parts

[Example 333]

(Production of colored composition (RM-134))

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 Filtered by a μm filter to produce a colored composition (RM-134) with a non-volatile content of 20% by 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 colored composition (RM-135))

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 A μm filter was used to produce a colored composition (RM-135) with a non-volatile content of 20% by mass.

Red colorant (RP-4): 12.0 parts

Acrylic resin solution 1: 19.2 parts

Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts

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

[Examples 335 to 337]

(Coloring composition (RM-136 to 138))

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

[Example 338]

(Coloring composition (RM-139)

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

[Example 339]

(Coloring composition (RM-140))

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

[Example 340]

(Coloring composition (RM-141))

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

[Example 341]

(Coloring composition (RM-142))

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

[Example 342 to Example 344]

(Coloring composition (RM-143 to 145))

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

[Example 345]

(Production of colored composition (RM-146))

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 Filtered by a μm filter to produce a colored composition (RM-146) with a non-volatile content of 20% by 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

[Examples 346 to 350, Examples 353 to 358]

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

Hereinafter, except that the composition shown in Table 5-4 was changed, a colored composition (RM-147 to 151, 154 to 159) was prepared in the same manner as the colored composition (RM-146).

[Example 351]

(Production of colored composition (RM-152))

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 Filtered by a μm filter to produce a colored composition (RM-152) with a non-volatile content of 20% by 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

Acid 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, a coloring composition (RM-153, 160, 161) was prepared in the same manner as the coloring composition (RM-152) except that the composition shown in Table 5-4 was changed.

[Comparative Example 2]

(Coloring composition (RCM-2): PR177)

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered by a μm filter to produce a colored composition (RCM-2) having a nonvolatile content of 20% by 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)

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered by a μm filter to produce a colored composition (RCM-4) having a nonvolatile content of 20% by 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)

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered by a μm filter to produce a colored composition (RCM-1) having a non-volatile content of 20% by 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)

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered by a μm filter to produce a colored composition (RCM-3) having a nonvolatile content of 20% by 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))

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered by a μm filter to produce a colored composition (RCM-5) having a nonvolatile content of 20% by 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)

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 A μm filter was used to produce a colored composition (YCM-1) having a non-volatile content of 20% by 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)

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered by a μm filter to produce a colored composition (YCM-2) having a nonvolatile content of 20% by 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)

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 A μm filter was used to produce a colored composition (YCM-3) having a nonvolatile content of 20% by 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))

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 3 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 A μm filter was used to produce a colored composition (YCM-4) with a non-volatile content of 20% by 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 colored composition)

The evaluation of the heat resistance, light resistance, coating film foreign matter, and storage stability of the obtained colored composition and the coating film produced using the colored composition was performed by the following method. The evaluation results are shown in Table 5.

(Evaluation of heat resistance)

Using a spin coater, apply the colored composition to a 100 mm × 100 mm, 1.1 mm thick glass substrate so that the dry film thickness becomes 2.0 μm, and then dry at 70 ° C. for 20 minutes, and then heat at 230 ° C. for 60 minutes. The substrate was left to cool, thereby preparing a coating film substrate (a state of a color filter). Using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.), the chromaticity of the obtained coating film under a C light source ((L ^* (1), a ^* (1), b ^* (1 )]). Furthermore, as a heat resistance test, it was heated at 250 ° C. for 1 hour, and the chromaticity ([L ^* (2), a ^* (2), b ^* (2)]) under a C light source was measured. The excellent difference ΔEab ^* was evaluated according to 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 (very 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 ^* 5.0 or more (very bad)

(Evaluation of light resistance)

A coating film substrate was prepared by the same method as in the evaluation of heat resistance, and the chromaticity under the C light source ([L ^* (1), a) was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). ^* (1), b ^* (1)]). Next, an ultraviolet cut filter ("COLORED OPTICAL GLASS L38" manufactured by HOYA) was attached to the substrate, and a 470 W / m ² xenon lamp was used to irradiate ultraviolet rays for 100 hours, and then the chromaticity under the C light source was measured ([ L ^* (2), a ^* (2), b ^* (2)]), the difference ΔEab ^{* was} obtained from the above calculation formula, and evaluation was performed on the same basis as heat resistance.

(Evaluation of coating foreign matter)

Using a spin coater, apply the colored composition to a 100 mm × 100 mm, 1.1 mm thick glass substrate so that the dry film thickness becomes 2.0 μm, and then dry at 70 ° C. for 20 minutes, and then heat at 230 ° C. for 60 minutes. Then, it was left to cool to prepare a coating film substrate. The evaluation was performed using a metal microscope "BX60" manufactured by Olympus System. The magnification is set to 500 times, and the number of particles that can be observed in any of the 5 fields of view through transmission counting is used. Evaluation was performed according to the following four levels.

◎: The number of foreign objects is less than 5 (very 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 (very bad)

(Storage stability test method)

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

◎: Viscosity change rate is less than 10% (very 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% (bad)

×: Viscosity change rate is 50% or more (very bad)

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

<Manufacturing method of the photosensitive coloring composition for color filters>

[Example 401]

(Photosensitive coloring composition (RR-1))

The following mixture (100 parts in total) was stirred and mixed to become uniform, and then filtered through a filter having a pore size of 1.0 μm to obtain a 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 Synthesis Corporation): 2.0 parts

Dipentaerythritol hexaacrylate

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

Ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (O-acetamidooxime)

Cyclohexanone: 39.0 parts

[Examples 402 to 567, Comparative Examples 4 to 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 brightness, contrast ratio, and film thickness of the obtained photosensitive coloring composition were evaluated by the following methods. The evaluation results are shown in Table 6. The evaluation of the transferability is shown in Table 7.

(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. The chromaticity of the obtained substrate became x = 0.683, y = 0.313 under the C light source. Coated substrate. The brightness (Y) of the obtained substrate was measured using a microspectrophotometer ("OSP-SP200" manufactured by Olympus Optical Co., Ltd.).

(Evaluation of Contrast Ratio (CR))

The contrast ratio was measured using a substrate on which the brightness was measured.

(Evaluation of film thickness)

The film thickness was measured using a substrate on which the brightness was measured. The film thickness was measured using a surface shape measuring instrument DEKTAK150 (manufactured by ULVAC ES).

(Evaluation of transferability)

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

◎: △ T is less than 0.5% (very good)

○: △ T 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 (very bad)

From the results in Table 6, it is clear that the examples using the coloring agent of the present invention are excellent in brightness and become thin films. In particular, a significant effect was confirmed by using C.I. Pigment Red 177, C.I. Pigment Red 269, or Azo Pigment 119, which was previously used as a blue-colored pigment.

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.

<Manufacturing method of green and blue photosensitive coloring composition for color filters>

(Green photosensitive coloring composition 1: PG58 / PY138)

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered with a μm to produce a green pigment dispersion having 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

The following mixture was stirred and mixed uniformly, and then dispersed using a pigment dispersion mill ("Minimodel M-250 MKII" manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then using a pore size of 5.0 The filter was filtered by a μm filter to prepare a yellow pigment dispersion having 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, the mixture of the following composition was stirred and mixed to make it uniform, and then filtered through a filter having a pore size of 1 μm to produce a 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 Synthesis Corporation): 2.0 parts

Dipentaerythritol hexaacrylate

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

Ethyl ketone, 1- [9-ethyl-6- (2-methylbenzylidene) -9H-carbazol-3-yl]-, 1- (0-acetamidooxime)

Cyclohexanone: 39.0 parts

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

Except changing the green colorant 1 (CI Pigment Green 58) 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.

Except changing green colorant 1 (CI Pigment Green 58) to purple colorant 1 (CI Pigment Violet 23), a purple pigment dispersion having a non-volatile content of 20% by mass was obtained in the same manner as the green pigment dispersion. body.

Next, 30.0 parts of a green pigment dispersion and 50.0 parts of a total of 18.0 parts of a yellow pigment dispersion were replaced with 46.0 parts of a blue dispersion and 50.0 parts of a total of 4.0 parts of a purple dispersion. In the same manner as in Composition 1, a blue photosensitive colored composition 1 was obtained.

<Production and Evaluation of Color Filters>

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

Then, by using the same method, a green photosensitive coloring composition 1 is used to form a green striped pixel near a red striped pixel. Furthermore, the blue photosensitive coloring composition 1 was used to similarly form blue striped pixels adjacent to the red and green pixels.

Then, a protective film is formed on a pixel composed of three colors of red, green, and blue using a photocurable resin composition. In this way, an RGB 3-color color filter with high brightness and excellent resistance can be produced.

Claims (9)

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 hydrogen An 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, Cyano, nitro, carboxy, sulfo, or halogen atoms; 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 hydrogen An 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 alkyl group which may have a substituent, an alkoxy group which may have a substituent, 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 which may have a substituent, -O-, -S-, -CO-,- SO _2- , -COO-, -CONH-, or -SO ₂ NH-.     A colorant for a color filter, comprising the azo pigment according to claim 1.         A coloring composition for a color filter, which contains at least a colorant and a binder resin, and the colorant is the colorant for a color filter according to claim 2.         The coloring composition for a color filter according to claim 3, further comprising a resin-based dispersant having an acidic substituent.         The coloring composition for a color filter according to claim 4, wherein the resin-based dispersant having an acidic substituent is a resin-based dispersant having an aromatic carboxyl group.         The coloring composition for a color filter according to claim 3, further comprising a pigment derivative including a pigment derivative having a basic substituent.     The coloring composition for a color filter according to claim 3, wherein the colorant further comprises a member 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, and lower. At least one of the group consisting of a yellow pigment represented by the general formula (3) and a 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, alkyl ammonium salts, phthalimidoiminomethyl groups which may have a substituent, or aminesulfonyl groups which may have a substituent ; 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 colored composition for a color filter according to claim 3, further comprising a photopolymerizable monomer.         A color filter is provided on a substrate with a filter segment formed of the coloring composition for a color filter according to any one of claims 3 to 8.