JP2014160160A - Color filter colorant, coloring composition and color filter - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a color filter colorant which is excellent in flowability and storage stability, provides high luminance when used for a color filter, exhibits preferable heat resistance and light fastness, and does not have coating foreign matter.SOLUTION: An azo pigment color filter colorant is represented by the general formula (1) specified in the figure.

Description

  The present invention relates to a color liquid crystal display device, a color filter colorant used in the production of a color filter used for a color image pickup tube element and the like, a color composition, and a color filter formed using the same.

In the liquid crystal display device, a liquid crystal layer sandwiched between two polarizing plates controls the amount of light passing through the first polarizing plate by controlling the degree of polarization of light passing through the first polarizing plate. The type using twisted nematic (TN) type liquid crystal is the mainstream. Other typical liquid crystal display device methods include an in-plane switching (IPS) method in which a pair of electrodes are provided on one substrate and electrolysis is applied in a direction parallel to the substrate,
Optically convendend which performs vertical alignment of nematic liquid crystal with negative dielectric anisotropy and optical compensation by making optical axes of uniaxial retardation films orthogonal to each other. There are bend (OCB) systems, etc., each of which has been put into practical use.

  A color filter has two or more kinds of fine band (striped) filter segments arranged in parallel or intersecting with each other on the surface of a transparent substrate such as glass, or the fine filter segments are arranged vertically and horizontally. It is made up of those arranged in The filter segments are as fine as several microns to several hundreds of microns, and are regularly arranged in a predetermined arrangement for each hue.

  In general, a color filter is produced by using a coloring composition in which a pigment is dispersed and a photocurable coloring composition containing a polyfunctional monomer, a polymerization initiator, an alkali-soluble resin and other components. In addition, a method of forming a colored pattern and a black matrix through a high temperature treatment process of 230 ° C. or higher is the mainstream.

  In recent years, color liquid crystal display devices, color image pickup tube elements, etc. have been widely used as home TVs, PC monitors, tablet terminals, and smartphones because they have been evaluated for space saving, light weight, and power saving. Yes. Along with this widespread use, in particular, there is a demand for higher brightness year by year, and in the color filter that is a constituent member, improvement in transmittance is desired. When a color filter with low luminance is used, the light transmittance is low, resulting in a dark screen. In order to obtain a bright screen, it is necessary to increase the number of backlights that are light sources. For this reason, from the viewpoint of suppressing an increase in power consumption, increasing the brightness of color filters has become a trend.

  The red filter segment, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate, generally has a diketopyrrolopyrrole pigment C.I. I. Pigment Red 254 is an anthraquinone pigment from the viewpoint of contrast ratio. I. Pigment Red 177 is used as the main pigment. Among these, C.I. I. Pigment Red 177 has a spectral transmittance of C.I. I. Since it is lower than CI Pigment Red 254 and the spectral shape is poor, C.I. I. As Pigment Red 177 was added, there was a problem of causing a decrease in luminance. Therefore, C.C. I. Development of an alternative material for Pigment Red 177 is desired.

  In Patent Documents 1 to 3, in order to further improve the luminance of the red filter segment, C.I. I. Pigment red 176, C.I. I. Pigment red 242, and C.I. I. It has been proposed to use an azo pigment such as CI Pigment Orange 38 as a main pigment, but sufficient luminance cannot be obtained, and further improvement has been demanded.

JP 2009-237462 A Japanese Patent Laid-Open No. 11-14824 Japanese Patent Laid-Open No. 10-115709

  The problems to be solved by the present invention are excellent in fluidity and storage stability when used in a coloring composition for a color filter, high brightness is obtained when used in a color filter, and heat resistance and light resistance are good. Then, it is providing the colorant for color filters without a coating-film foreign material, a coloring composition, and a color filter using the same.

  As a result of intensive studies, the present inventor has found that the above problems can be solved by using an azo pigment having a specific structure as a colorant for a color filter, and has reached the present invention.

  That is, an embodiment of the present invention relates to a color filter colorant comprising an azo pigment represented by the following general formula (1).

General formula (1)

[In General Formula (1), R _a and R _b each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent. R _c represents an alkyl group having 1 to 4 carbon atoms. X and Y each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or a trifluoromethyl group. ]

  Moreover, the embodiment of the present invention further relates to the colorant for a color filter, further comprising a pigment derivative.

  An embodiment of the present invention also relates to a color filter coloring composition comprising at least a colorant and a binder resin, wherein the colorant is the color filter colorant. .

  The embodiment of the present invention further includes C.I. I. Pigment red 254, C.I. I. C. I. Pigment Red 242 and / or brominated diketopyrrolopyrrole pigment is contained, The present invention relates to the coloring composition for a color filter.

  In addition, the embodiment of the present invention further relates to the coloring composition for a color filter, further comprising a photopolymerizable monomer.

  An embodiment of the present invention also relates to a color filter comprising a filter segment formed from the color filter coloring composition.

  By using the colorant of the present invention, it is possible to provide a color filter that is excellent in luminance, heat resistance, and light resistance.

Hereinafter, the present invention will be described in detail.
Note that “CI” described below means a color index (CI).

<Colorant for color filter (colorant)>
First, a color filter colorant comprising an azo pigment represented by the general formula (1) of the present invention will be described. In the present specification, “azo pigment represented by the general formula (1)” is sometimes abbreviated as “pigment”, and “colorant for color filter” is sometimes abbreviated as “colorant”.

  In general formula (1), examples of the halogen atom include a fluorine atom, a chlorine atom, and a bromine atom. Preferably, it is a chlorine atom.

  The alkyl group having 1 to 4 carbon atoms may be linear or branched, and specifically includes methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert- A butyl group is mentioned. Preferably, it is a methyl group.

The alkoxy group having 1 to 4 carbon atoms may be linear or branched. Specifically, methoxy group, ethoxy group, propoxy group, isopropoxy group, butoxy group, isobutoxy group, sec-butoxy group, tert -A butoxy group is mentioned. Preferably, it is a methoxy group.

Examples of the substituent in the phenyl group which may have a substituent include the above halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxycarbonyl group having 2 to 4 carbon atoms such as a trifluoromethyl group and a methoxycarbonyl group. The substituents may be bonded to each other by a divalent group such as a ureyl group (—NHCONH—) to form a ring such as a benzimidazolone ring.

As the colorant of the present invention, it is preferable that either R _a or R _b is a phenyl group from the viewpoint of luminance. R _c is preferably a methyl group. Further, either X or Y is preferably a chlorine atom.

  The colorant of the present invention may have a chemical structure of the general formula (1) or a tautomer thereof, and may be a pigment having any crystal form, and any crystal called a so-called polymorph. It may be a mixed crystal of pigments having a form. The crystal form of these pigments can be confirmed by powder X-ray diffraction measurement or X-ray crystal structure analysis.

Specific examples of the colorant of the present invention include azo pigments shown in Table 1 below, but the present invention is not limited thereto. In Table 1, Ph represents a phenyl group, and C ₄ H ₉ represents a butyl group.

(Method for producing colorant)
As the colorant of the present invention, as is well known in the pigment field, there are mainly known two production methods (A) and (B), but the present invention is not limited to these. is not.

Method (A) is a method in which a carboxylic acid chloride of an azo compound represented by the following general formula (2) is subjected to a condensation reaction with a diamine represented by the general formula (3) at a molar ratio of 2: 1.
General formula (2)

General formula (3)

[In General Formulas (2) and (3), R _a , R _b , R _c , X, and Y are as defined in General Formula (1). ]

In another method (B), an amine represented by the following general formula (4) (diazo component) and dinaphthol (coupling component) represented by general formula (5) are mixed at a molar ratio of 2: 1. In this method, the coupling reaction is performed.
General formula (4)

General formula (5)

[In the general formulas (4) and (5), R _a , R _b , R _c , X, and Y have the same meanings as in the general formula (1). ]

  The carboxylic acid chloride represented by the general formula (2) is subjected to a coupling reaction between a diazo compound (general formula (6)) of an amine represented by the general formula (4) and 2-hydroxy-3-naphthoic acid. The carboxylic acid derivative of the azo compound obtained in this way can be obtained by chlorination.

General formula (6)

[In the general formula (6), R _a , R _b and R _c have the same _{meaning as} in the general formula (1). Z ⁻ represents an inorganic or organic anion. ]

Examples of the amine represented by the general formula (4) include the following compounds.
4-methoxy-3-amino-benzoic acid amide,
4-methoxy-3-amino-benzoic acid methylamide,
4-methoxy-3-amino-benzoic acid ethylamide,
4-methoxy-3-amino-benzoic acid propylamide,
4-methoxy-3-amino-benzoic acid butyramide,
4-methoxy-3-amino-benzoic acid dimethylamide,
4-methoxy-3-amino-benzoic acid diethylamide,
4-methoxy-3-amino-benzoic acid di-n-propylamide,
4-methoxy-3-amino-benzoic acid di-n-butyramide,
4-methoxy-3-amino-benzoic acid anilide,
4-methoxy-3-amino-benzoic acid- (3′-chloro) -anilide,
4-methoxy-3-amino-benzoic acid- (3′-methyl) -anilide,
4-methoxy-3-amino-benzoic acid- (3′-methoxy) -anilide,
4-methoxy-3-amino-benzoic acid- (3′-trifluoromethyl) -anilide,
4-methoxy-3-amino-benzoic acid- (2 ′ · 5′-dichloro) -anilide,
4-methoxy-3-amino-benzoic acid- (2′-chloro-5′-trifluoromethyl) -anilide,
4-methoxy-3-amino-benzoic acid- (2'-chloro-5'-methyl) -anilide,
4-methoxy-3-amino-benzoic acid- (2'-chloro-5'-methoxy) -anilide,
4-methoxy-3-amino-benzoic acid- (3′-cyano) -anilide,
4-methoxy-3-amino-benzoic acid- (3′-nitro) -anilide,
4-methoxy-3-amino-benzoic acid- (2′-methyl-5′-carbomethoxy) -anilide,
4-ethoxy-3-amino-benzoic acid amide,
4-ethoxy-3-amino-benzoic acid methylamide,
4-ethoxy-3-amino-benzoic acid ethylamide,
4-ethoxy-3-amino-benzoic acid propylamide,
4-ethoxy-3-amino-benzoic acid butyramide,
4-ethoxy-3-amino-benzoic acid dimethylamide,
4-ethoxy-3-amino-benzoic acid diethylamide,
4-ethoxy-3-amino-benzoic acid di-n-propylamide,
4-ethoxy-3-amino-benzoic acid di-n-butyramide,
4-ethoxy-3-amino-benzoic acid anilide,
4-ethoxy-3-amino-benzoic acid amide,
4-propoxy-3-amino-benzoic acid methylamide,
4-propoxy-3-amino-benzoic acid ethylamide,
4-propoxy-3-amino-benzoic acid propylamide,
4-propoxy-3-amino-benzoic acid butyramide,
4-propoxy-3-amino-benzoic acid dimethylamide,
4-propoxy-3-amino-benzoic acid diethylamide,
4-propoxy-3-amino-benzoic acid di-n-propylamide,
4-propoxy-3-amino-benzoic acid di-n-butyramide,
4-butoxy-3-amino-benzoic acid anilide,
4-butoxy-3-amino-benzoic acid methylamide,
4-butoxy-3-amino-benzoic acid ethylamide,
4-butoxy-3-amino-benzoic acid propylamide,
4-butoxy-3-amino-benzoic acid butyramide,
4-butoxy-3-amino-benzoic acid dimethylamide,
4-butoxy-3-amino-benzoic acid diethylamide,
4-butoxy-3-amino-benzoic acid di-n-propylamide,
4-butoxy-3-amino-benzoic acid di-n-butyramide,
4-Butoxy-3-amino-benzoic acid anilide.

  The carboxylic acid chloride is obtained by reacting a corresponding carboxylic acid using a chlorinating agent. The chlorinating agent is phosphorus pentachloride, phosphorus trichloride, preferably thionyl chloride.

  When synthesizing the carboxylic acid chloride, it is preferable to dry the carboxylic acid of the corresponding azo compound in advance or remove water by azeotropic distillation in an organic solvent.

  The chlorination reaction is preferably performed in, for example, pyridine, dimethylformamide, monochlorobenzene, dichlorobenzene, toluene, xylene, trimethylbenzene, nitrobenzene, or thionyl chloride. When using other than pyridine or dimethylformamide, it is preferable to use pyridine or dimethylformamide in combination.

The carboxylic acid chloride of the azo compound represented by the general formula (2) is condensed with the diamine represented by the formula (3) at a molar ratio of 2: 1. Examples of the diamine include the following compounds.
1,4-phenylenediamine,
2-methyl-1,4-phenylenediamine,
2-methoxy-1,4-phenylenediamine,
2-trifluoromethyl-1,4-phenylenediamine,
2-chloro-1,4-phenylenediamine,
2-nitro-1,4-phenylenediamine,
2-cyano-1,4-phenylenediamine,
2,5-dichloro-1,4-phenylenediamine,
2,5-dimethyl-1,4-phenylenediamine,
2,5-dimethoxy-1,4-phenylenediamine,
2-methyl-5-chloro-1,4-phenylenediamine,
2-methoxy-5-chloro-1,4-phenylenediamine,
2-trifluoromethyl-5-chloro-1,4-phenylenediamine.

  The condensation reaction between the carboxylic acid chloride and the diamine is preferably performed in an anhydrous solvent. Specific examples include pyridine, dimethylformamide, monochlorobenzene, dichlorobenzene, toluene, xylene, trimethylbenzene, and nitrobenzene.

  In addition, it is preferable to isolate the carboxylic acid chloride to be used, but it is also possible to carry out the condensation reaction directly without this isolation step.

  Dinaphthol represented by the general formula (5) is trichloride from 2-hydroxy-3-naphthoic acid and a diamine represented by the general formula (3) in an anhydrous solvent such as toluene, xylene, chlorobenzene and the like. It can be obtained by a known method using phosphorus or the like.

  The coupling reaction is performed by adding an alkaline solution of the coupling component to the acidic solution of the diazonium salt. The alkali metal hydroxide, such as sodium hydroxide, used to dissolve the coupling component is preferably in an amount sufficient to neutralize the acid liberated from the diazonium salt.

  The diazonium salt can be obtained by diazotizing the amine represented by the general formula (4) with nitrous acid, nitrite or nitrite in an acidic aqueous solution to which hydrochloric acid, sulfuric acid, acetic acid or the like is added.

  The coupling reaction is preferably performed in the pH range of 4 to 6, and a buffer solution such as acetic acid may be used at that time.

  The coupling reaction is performed in the range of 5 to 100 ° C., and the reaction proceeds rapidly. Further, since the obtained azo pigment is highly insoluble, it can be easily isolated from unreacted substances and by-products by filtration, and a highly pure pigment can be obtained.

  The coupling reaction can also be performed in the presence of a lubricant, a dispersant, or an emulsifier.

(Miniaturization of pigment (color filter colorant))
In order to obtain high brightness and high contrast when the pigment constituting the colorant for color filter of the present invention is a colored composition, the pigment particles are refined by salt milling or acid pasting treatment as necessary. By applying, it can be suitably used as a color filter pigment. The primary particle diameter of the pigment is preferably 10 nm or more and 50 nm or less.

  Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent is heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt works as a crushing aid, and it is thought that the pigment is crushed using the high hardness of the inorganic salt during salt milling, thereby generating an active surface and causing crystal growth. Yes. Accordingly, during kneading, the pigment is crushed and crystal growth occurs simultaneously, and the primary particle diameter of the pigment obtained varies depending on the kneading conditions.

  In order to promote the crystal growth of the pigment by heating, the heating temperature is preferably 35 to 150 ° C. The kneading time for the salt milling is preferably 2 to 24 hours in view of the balance between the particle size distribution of the primary particles of the salt milled and the cost required for the salt milling.

  By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution in which the primary particle diameter is very fine and the width of the distribution is wide. In particular, it is preferable to use a pigment derivative in combination.

  As the water-soluble inorganic salt used for salt milling, sodium chloride, barium chloride, potassium chloride, sodium sulfate and the like can be used, but sodium chloride (salt) is preferably used from the viewpoint of cost. The water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, and most preferably 300 to 1200 parts by mass with respect to 100 parts by mass of the pigment, from the viewpoint of both processing efficiency and production efficiency.

  The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt to be used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, those having a high boiling point of 120 ° C. or higher are preferable from the viewpoint of safety. Such as, for example, 2-methoxyethanol, 2-butoxyethanol, 2- (isopentyloxy) ethanol, 2- (hexyloxy) ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol , Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. Is used. These water-soluble organic solvents are preferably used in an amount of 5 to 1000% by weight, and most preferably 50 to 500% by weight, based on the total weight of the pigment (100% by weight).

(Dye derivative)
Hereinafter, although the specific example of the pigment derivative used for this invention is described, this invention is not limited to these. However, in the formula, C ₄ H ₉ is a butyl group, C ₃ H ₇ is a prokyl group, i-C ₃ H ₇ is an isopropyl group, C ₂ H ₄ is an ethylene group, and C ₃ H ₆ is a 1,3-propylene group. Represents.

(Specific examples of benzoisoindole derivatives)
As the benzoisoindole derivative, specifically, a compound represented by the following formula (7) can be used, but is not limited thereto.

(Specific examples of anthraquinone derivatives)
Specifically as an anthraquinone derivative, the compound represented by following formula (8) can be used, However, It is not limited to these.

(Specific examples of dianthraquinone derivatives)
As the dianthraquinone derivative, specifically, a compound represented by the following formula (9) can be used, but is not limited thereto.

(Specific examples of thiazine indigo derivatives)
As the thiazineindigo derivative, specifically, a compound represented by the following formula (10) can be used, but is not limited thereto.

(Specific examples of azo dye derivatives)
As the azo dye derivative, specifically, a compound represented by the following formula (11), formula (12), or formula (13) can be used, but is not limited thereto.

(Specific examples of quinophthalone derivatives)
As the quinophthalone derivative, specifically, compounds represented by the following formulas (14-1) to (14-13) can be used, but are not limited thereto.

(Specific examples of quinacridone derivatives)
As the quinacridone derivative, specifically, a compound represented by the following formula (15) can be used, but is not limited thereto.

(Specific examples of diketopyrrolopyrrole derivatives)
As the diketopyrrolopyrrole derivative, specifically, a compound represented by the following formula (16) or formula (17) can be used, but is not limited thereto.

(Specific examples of naphthol derivatives)
As the naphthol derivative, specifically, a compound represented by the following formula (18) can be used, but is not limited thereto.

  These dye derivatives are preferably used in an amount of 2 to 30% by weight, and most preferably 5 to 20% by weight, based on the total weight of the pigment (100% by weight).

  When the salt is milled, a resin may be added as necessary. Here, 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 solid at room temperature, preferably insoluble in water, and more preferably partially soluble in the water-soluble organic solvent. The amount of resin used is preferably in the range of 2 to 200% by weight based on the total weight of the pigment (100% by weight).

(Other pigments)
The coloring composition for a color filter of the present invention may be used in combination with other coloring matter such as a pigment or a dye other than the coloring agent of the present invention within a range not impairing the effects of the present invention in order to adjust chromaticity.

  For example, C.I. I. 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, 270, 272, 273, 274, 276, 277, 278, Mention may be made of red pigments such as 279, 280, 281, 282, 283, 284, 285, 286 or 287. Examples of red dyes include xanthene series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, and anthraquinone series. Specifically, C.I. I. And salt forming compounds of xanthene acid dyes such as Acid Red 52, 87, 92, 289 and 338.

  In addition, C.I. I. Pigment orange 43, 71, or 73 and / or C.I. I. 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, or a yellow pigment 221 and the like can be used in combination. Examples of the orange dye and / or yellow dye include quinoline series, azo series (pyridone series, barbituric acid series, metal complex series, etc.), disazo series, and methine series.

  Preferred dyes to be used in combination include azo dyes, naphtholazo dyes, diketopyrrolopyrrole dyes, anthraquinone dyes, quinophthalone dyes, and perylene dyes from the viewpoint of luminance. Specifically, C.I. I. Pigment red 176, 177, 254, 242, C.I. I. Pigment Yellow 138, 139, 150, 185, brominated diketopyrrolopyrrole pigments. Among these, particularly preferred dyes are C.I. I. Pigment red 254, C.I. I. Pigment Red 242, and brominated diketopyrrolopyrrole pigments.

  When the above-mentioned other pigments are used in combination with the colorant of the present invention, the colorant of the present invention is preferably in the range of 10% by weight to 100% by weight in the total amount of the colorant (100% by weight). More preferably, it is in the range of 30% by weight to 100% by weight. When the colorant of the present invention is 10% by mass or less, the effect of excellent luminance cannot be sufficiently exhibited.

<Coloring composition for color filter>
The coloring composition for a color filter of the present invention is composed of a binder resin and an organic solvent in addition to the colorant described above.
(Binder resin)
Examples of the binder resin contained in the colored composition for a color filter of the present invention include conventionally known thermoplastic resins and thermosetting resins.

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

  When used as a coloring composition for a color filter, the spectral transmittance is preferably 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm in the visible light region. Moreover, when using with the form of an alkali image development type colored resist, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic group containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an energy ray curable resin having an ethylenically unsaturated active double bond can also be used.

  Examples of the alkali-soluble resin obtained by copolymerizing an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, or Examples include isobutylene / (anhydrous) maleic acid copolymer. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

  Energy ray curable resins having ethylenically unsaturated active double bonds include reactive substitution of isocyanate groups, aldehyde groups, epoxy groups, etc. on polymers having reactive substituents such as hydroxyl groups, carboxyl groups, amino groups, etc. A resin in which a photo-crosslinkable group such as a (meth) acryloyl group or a styryl group is introduced into the polymer by reacting a (meth) acrylic compound having a group or cinnamic acid is used. In addition, polymers containing acid anhydrides such as styrene-maleic anhydride copolymer and α-olefin-maleic anhydride copolymer are half-esterified with a (meth) acrylic compound having a hydroxyl group such as hydroxyalkyl (meth) acrylate. A modified version is also used.

  A thermoplastic resin having both alkali-soluble performance and energy ray curing performance is also preferable as the photosensitive coloring composition for color filters.

  The following are mentioned as a monomer which comprises the said thermoplastic resin. For example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) Acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, or ethoxypolyethylene Glycol (meth) acrylate of (meth) acrylates,

  Alternatively, (meth) acrylamide (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, acryloylmorpholine, etc. Acrylamides, styrenes, styrenes such as α-methylstyrene, ethyl vinyl ethers, n-propyl vinyl ethers, isopropyl vinyl ethers, n-butyl vinyl ethers, vinyl ethers such as isobutyl vinyl ethers, fatty acid vinyls such as vinyl acetate or vinyl propionate Kind.

  Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide Coumarin, 4,4′-bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidophenyl) methane, N, N′-1,3-phenylenedimaleimide, N, N′-1,4- Phenylene dimaleimide, N- (1-pyrenyl) maleimide, N- (2,4,6-trichlorophenyl) maleimide, N- (4-aminophenyl) maleimide, N- (4-nitrophenyl) maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-sc N-imidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N- [4- (2-benzimidazolyl) phenyl N-substituted maleimides such as maleimide and 9-maleimide acridine.

  In particular, it is preferable to have a structural unit derived from an N-substituted maleimide, and among them, cyclohexylmaleimide, methylmaleimide, ethylmaleimide, and 1,2-bismaleimideethane are preferable from the viewpoint of heat resistance, and cyclohexylmaleimide is particularly preferable.

  Examples of the thermosetting resin include epoxy resin, benzoguanamine resin, rosin-modified maleic acid resin, rosin-modified fumaric acid resin, melamine resin, urea resin, and phenol resin.

  The coloring composition for a color filter of the present invention preferably includes a thermosetting resin in terms of heat resistance, for example, among them, an epoxy resin and a melamine resin can be more suitably used, and a melamine resin is particularly preferable. Of these, a melamine compound having a methylolimino group or a condensate thereof is more preferable.

  The thermosetting resin is preferably added in the range of 5 to 60 parts by weight with respect to 100 parts by weight of the colorant. If the amount is less than 10 parts by weight, the effect of improving heat resistance and light resistance is reduced, and if it exceeds 60 parts by weight, the developability deteriorates during alkali development, which is not preferable.

  The weight average molecular weight (Mw) of the binder resin is preferably in the range of 5,000 to 100,000, more preferably in the range of 8,000 to 50,000 in order to disperse the colorant preferably. The number average molecular weight (Mn) is preferably in the range of 2,500 to 50,000, and the value of Mw / Mn is preferably 10 or less.

  Here, the weight average molecular weight (Mw) and the number average molecular weight (Mn) are connected to four separation columns in series in the gel permeation chromatography “HLC-8120GPC” manufactured by Tosoh Corporation. This is a polystyrene equivalent molecular weight measured using “TSK-GEL SUPER H5000”, “H4000”, “H3000”, and “H2000” manufactured by the company and using tetrahydrofuran as the mobile phase.

  When using a binder resin as a coloring composition for a color filter, from the viewpoint of dispersibility, developability, and heat resistance, a carboxyl group, a pigment carrier, and an organic solvent that act as a pigment adsorbing group and an alkali-soluble group during development. The balance between the aliphatic group and aromatic group acting as an affinity group for is important for dispersibility, developability, and durability, and it is preferable to use a resin having an acid value of 20 to 300 mgKOH / g. When the acid value is less than 20 mgKOH / g, the solubility in the developing solution is poor and it is difficult to form a fine pattern. When it exceeds 300 mgKOH / g, no fine pattern remains.

  The binder resin can be used in an amount of 20 to 500% by weight based on the total weight of the colorant. If it is less than 30% by weight, the film formability and various resistances are insufficient, and if it exceeds 500% by weight, the pigment concentration is low and color characteristics cannot be expressed.

(Organic solvent)
In the coloring composition of the present invention, a colorant is sufficiently dispersed and permeated in a carrier, and applied to a glass substrate or the like so as to have a dry film thickness of 0.2 to 5 μm to form a filter segment. An organic solvent can be included to facilitate this.

  Examples of the organic solvent include ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl -1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m -Diethylbenzene, m-dichlorobenzene, N, N-dimethylacetamide, N, N- Methylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, Ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol Monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate , Diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether Dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol mono Ethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, Louis Seo ketone, methyl cyclohexanol, acetic acid n- amyl acetate n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

  Among them, because of good dispersion of the colorant of the present invention, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, benzyl It is preferable to use aromatic alcohols such as alcohol and ketones such as cyclohexanone.

  An organic solvent can be used individually by 1 type or in mixture of 2 or more types. Moreover, since the solvent can adjust the coloring composition to an appropriate viscosity and can form a filter segment with a desired uniform film thickness, the total weight of the colorant is 100% by weight (500% to 4000% by weight). It is preferable to use it in the quantity.

(Dispersing aid)
When dispersing the colorant in the carrier, a dispersion aid such as a pigment derivative, a resin-type dispersant, or a surfactant can be appropriately used. Since the dispersion aid is excellent in dispersion of the colorant and has a great effect of preventing reaggregation of the colorant after dispersion, a coloring composition obtained by dispersing the colorant in the carrier using the dispersion aid was used. In this case, a color filter having a high spectral transmittance can be obtained.

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

(Resin type dispersant)
The resin-type dispersant has a pigment-affinity part that has the property of adsorbing to the colorant and a part that is compatible with the carrier, and functions to adsorb to the colorant and stabilize dispersion on the carrier. It is. Specific examples of resin-type dispersants include polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, and polycarboxylic acid alkylamine salts. , Polysiloxane, long-chain polyaminoamide phosphate, hydroxyl group-containing polycarboxylic acid ester, modified products thereof, amides formed by reaction of poly (lower alkyleneimine) and polyester having a free carboxyl group, and salts thereof Oil-soluble dispersants such as, (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Resin, water-soluble polymer, polyester, modified poly Acrylate-based, ethylene oxide / propylene oxide adduct, phosphoric ester or the like is used, they may be used alone or in combination, it is not necessarily limited thereto.

  Among the above dispersants, a polymer dispersant having a basic functional group is preferred because the viscosity of the dispersion is reduced by a small addition amount and high contrast is exhibited, and a nitrogen atom-containing graft copolymer or side chain is preferred. A nitrogen atom-containing acrylic block copolymer and a urethane polymer dispersant having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, and the like are preferable.

  The resin-type dispersant is preferably used in an amount of about 5 to 200% by weight based on the total amount of the colorant, and more preferably about 10 to 100% by weight from the viewpoint of film formability.

  Commercially available resin-type dispersants include Dsperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170 manufactured by Big Chemie Japan. 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 SOLPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000 manufactured by Nihon Lubrizol Corporation, such as Lactimon, Lactimon-WS or Bykumen. 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., Ciba Japan EFKA-46, 47, 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, 755 , 1101,120,150,1501,1502,1503, etc., Ajinomoto Fine-Techno Co., Ltd. of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

(Surfactant)
Surfactants include sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate , Anionic surfactants such as monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate ester, Polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Nonionic surfactants such as alkyl ether phosphates, polyoxyethylene sorbitan monostearate and polyethylene glycol monolaurate, chaotic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts, alkyldimethylamino Examples include amphoteric surfactants such as alkylbetaines such as betaine acetate and alkylimidazolines, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

  The amount of the resin-type dispersant and surfactant added is preferably 0.1 to 55% by weight, more preferably 0.1 to 45% by weight, based on the total amount of the colorant (100% by weight). It is. When the blending amount of the resin-type dispersant and the surfactant is less than 0.1% by weight, it is difficult to obtain the added effect. When the blending amount is more than 55% by weight, the dispersion is adversely affected by the excessive dispersant. May affect.

(Method for producing colored composition)
The coloring composition of the present invention is produced by dispersing a mixture of a colorant, a binder resin, and an organic solvent using various dispersing machines such as a three-roll mill, a two-roll mill, a sand mill, a kneader, or an attritor. can do. Moreover, the coloring composition of this invention can also be manufactured by mixing the colorant separately dispersed in a binder resin and an organic solvent.

  In this way, when the colorant is dispersed in the binder resin using a disperser, the dispersed particle size becomes smaller as the dispersion proceeds, the transparency increases, and the contrast ratio increases. In particular, good characteristics can be obtained from about 300 nm. On the other hand, when the dispersion progresses and the dispersed particle size becomes small, the viscosity of the dispersion increases and the thixotropic property tends to increase. When used as a photosensitive coloring composition for a color filter, it is required to have a low viscosity and a Newtonian flow because it is required to be coated with a thin film and to have a smooth coating surface. For this reason, it is preferable to suppress the dispersed particle size to about 100 nm in consideration of the viscosity and thixotropic property preferable for normal use. Thus, by using a colorant having an average primary particle size of 100 nm or less and controlling the degree of dispersion so that the average particle size of the dispersed particles is in the range of 50 nm to 150 nm, the increase in viscosity and thixotropic property are minimized. Thus, a good pigment dispersion can be obtained.

(Removal of coarse particles)
The colored composition for color filter is subjected to centrifugal separation or filtration using a sintered filter, a membrane filter or the like, so that coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that a coloring composition does not contain a particle | grain of 0.5 micrometer or more substantially. More preferably, it does not contain particles of 0.3 μm or less.

<Photosensitive coloring composition for color filter>
The coloring composition for color filters can be used as a photosensitive coloring composition for color filters by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

(Photopolymerizable monomer)
Photopolymerizable monomers that can be added to the color filter coloring composition include monomers or oligomers that are cured by ultraviolet rays or heat to produce a transparent resin, and these are used alone or in combination of two or more. It can be used by mixing. The amount of the monomer is preferably 5 to 400% by weight based on the total weight of the colorant (100% by weight), and more preferably 10 to 300% by weight from the viewpoint of photocurability and developability. preferable.

  Examples of monomers and oligomers that are cured by ultraviolet rays or heat to produce a transparent resin include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, and 2-hydroxypropyl (meth) acrylate. , Cyclohexyl (meth) acrylate, β-carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, triethylene glycol di (meth) acrylate, tripropylene glycol di ( (Meth) acrylate, trimethylolpropane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanediol diglycy 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, tricyclodeca Nyl (meth) acrylate, ester acrylate, methylolated melamine (meth) acrylate ester, epoxy (meth) acrylate, urethane acrylate and other acrylic esters and methacrylate esters, (meth) acrylic acid, styrene, vinyl acetate, Hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxymethyl Examples include, but are not necessarily limited to, til (meth) acrylamide, N-vinylformamide, acrylonitrile and the like.

(Photopolymerization initiator)
When the photosensitive coloring composition for color filters is cured by ultraviolet irradiation and a filter segment is formed by a photolithographic method, a photopolymerization initiator or the like is added to add a photopolymerization initiator or the like to a solvent developing type or alkali developing type coloring resist material. It can be prepared in the form. The blending amount when using the photopolymerization initiator is preferably 2 to 200% by weight based on the total amount of the colorant, and 5 to 150% by weight from the viewpoint of photocurability and developability. More preferred.

  Examples of the photopolymerization initiator include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1- Hydroxycyclohexyl phenyl ketone, 2-methyl-1- [4- (methylthio) phenyl] -2-morpholinopropan-1-one, 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1 Acetophenone compounds such as-[4- (4-morpholinyl) phenyl] -1-butanone or 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one; benzoin, benzoin Methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or Benzoin compounds such as benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone Thioxanthone compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-meth) Cyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloro Methyl) -s-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2 -(4-Methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- Triazine compounds such as (4′-methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxy) )], Or oxime ester compounds such as O- (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6 Phosphine compounds such as trimethylbenzoyl) phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; A carbazole compound; an imidazole compound; or a titanocene compound is used.

  These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required. These photopolymerization initiators are preferably 2 to 200% by weight based on the total amount of the colorant in the color filter coloring composition (100% by weight), and 5 from the viewpoint of photocurability and developability. More preferably, it is -150 weight%.

(Sensitizer)
Furthermore, the photosensitive coloring composition for a color filter of the present invention can contain a sensitizer.

  Sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives , Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, Azulene derivatives, azurenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, Trapirazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine Derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl Anthraquinone, 4,4'-diethylisophthalophenone, 3,3 'or 4,4'-tetra (t-butylperoxycarbonyl) benzo Phenone, 4,4'-diethylaminobenzophenone, etc. are mentioned.

  More specifically, edited by Shin Okawara et al., “Dye Handbook” (1986, Kodansha), edited by Shin Okawara et al., “Chemistry of Functional Dye” (1981, CMC), edited by Tadasaburo Ikemori et al. Examples include, but are not limited to, sensitizers described in "Special Functional Materials" (1986, CMC). In addition, a sensitizer that absorbs light from the ultraviolet region to the near infrared region can also be contained.

  Two or more kinds of sensitizers may be used in any ratio as required. The blending amount when using the sensitizer is preferably 3 to 60% by weight based on the total weight of the photopolymerization initiator contained in the colored composition (100% by weight). From the viewpoint of developability, it is more preferably 5 to 50% by weight.

(Amine compounds)
Moreover, the coloring composition for color filters of this invention can be made to contain the amine compound which has a function which reduces the dissolved oxygen.

  Such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminobenzoate. Examples include ethyl, 2-ethylhexyl 4-dimethylaminobenzoate, and N, N-dimethylparatoluidine.

(Leveling agent)
In order to improve the leveling property of the composition on the transparent substrate, it is preferable to add a leveling agent to the coloring composition for a color filter of the present invention. As the leveling agent, dimethylsiloxane having a polyether structure or a polyester structure in the main chain is preferable. Specific examples of dimethylsiloxane having a polyether structure in the main chain include FZ-2122 manufactured by Toray Dow Corning, BYK-333 manufactured by Big Chemie. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK Chemie. Dimethylsiloxane having a polyether structure in the main chain and dimethylsiloxane having a polyester structure in the main chain can be used in combination. In general, the leveling agent content is preferably 0.003 to 0.5% by weight based on the total weight of the coloring composition (100% by weight).

  Particularly preferred as a leveling agent is a kind of so-called surfactant having a hydrophobic group and a hydrophilic group in the molecule, having a hydrophilic group but low solubility in water, and when added to a coloring composition, It has the characteristics of low surface tension reduction ability, and it is useful to have good wettability to the glass plate despite its low surface tension reduction ability. Those that can sufficiently suppress the chargeability can be preferably used. As a leveling agent having such preferable characteristics, dimethylpolysiloxane having a polyalkylene oxide unit can be preferably used. Examples of the polyalkylene oxide unit include a polyethylene oxide unit and a polypropylene oxide unit, and dimethylpolysiloxane may have both a polyethylene oxide unit and a polypropylene oxide unit.

  In addition, the bonding form of the polyalkylene oxide unit with dimethylpolysiloxane includes a pendant type in which the polyalkylene oxide unit is bonded in the repeating unit of dimethylpolysiloxane, a terminal-modified type in which the end of dimethylpolysiloxane is bonded, and dimethylpolysiloxane. Any of linear block copolymer types in which they are alternately and repeatedly bonded may be used. Dimethylpolysiloxane having a polyalkylene oxide unit is commercially available from Toray Dow Corning Co., Ltd., for example, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, FZ. -2207, but is not limited thereto.

  An anionic, cationic, nonionic or amphoteric surfactant can be supplementarily added to the leveling agent. Two or more kinds of surfactants may be mixed and used.

  Anionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, alkyl diphenyl ether disulfonic acid Sodium, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate Examples include esters.

  Examples of the chaotic surfactant that is supplementarily added to the leveling agent include alkyl quaternary ammonium salts and their ethylene oxide adducts. Nonionic surfactants added to the leveling agent as auxiliary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, polyoxyethylene sorbitan monostearate And amphoteric surfactants such as alkyl dimethylamino acetic acid betaine and alkylimidazolines, and fluorine-based and silicone-based surfactants.

(Curing agent, curing accelerator)
Moreover, in order to assist hardening of a thermosetting resin, the coloring composition for color filters of this invention may contain the hardening | curing agent, the hardening accelerator, etc. as needed. As the curing agent, phenolic resins, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds and the like are effective, but are not particularly limited to these, and thermosetting resins. Any curing agent may be used as long as it can react with the. Among these, a compound having two or more phenolic hydroxyl groups in one molecule and an amine curing agent are preferable. Examples of the curing accelerator include amine compounds (for example, dicyandiamide, benzyldimethylamine, 4- (dimethylamino) -N, N-dimethylbenzylamine, 4-methoxy-N, N-dimethylbenzylamine, 4-methyl). -N, N-dimethylbenzylamine etc.), quaternary ammonium salt compounds (eg triethylbenzylammonium chloride etc.), blocked isocyanate compounds (eg dimethylamine etc.), imidazole derivative bicyclic amidine compounds and salts thereof (eg Imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1- (2-cyanoethyl) -2- D Ru-4-methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), guanamine compounds (eg, melamine, guanamine, acetoguanamine, benzoguanamine, etc.), S-triazine derivatives (eg, 2,4-diamino-6) -Methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6 Methacryloyloxyethyl-S-triazine / isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. As content of the said hardening accelerator, 0.01 to 15 weight% is preferable with respect to the thermosetting resin whole quantity.

(Other additive components)
The coloring composition for a color filter of the present invention can contain a storage stabilizer in order to stabilize the viscosity with time of the composition. Moreover, in order to improve adhesiveness with a transparent substrate, adhesion improving agents, such as a silane coupling agent, can also be contained.

  Examples of storage stabilizers include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid, and methyl ethers thereof, t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Organic phosphines, phosphites and the like can be mentioned. The storage stabilizer can be used in an amount of 0.1 to 10% by weight based on the total amount of the colorant (100% by weight).

  Examples of the adhesion improver include vinyl silanes such as vinyltris (β-methoxyethoxy) silane, vinylethoxysilane and vinyltrimethoxysilane, (meth) acrylsilanes such as γ-methacryloxypropyltrimethoxysilane, β- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) methyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane, β- (3,4-epoxycyclohexyl) Epoxysilanes such as methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, N-β (aminoethyl) γ-aminopropyltrimethoxysilane, N-β (amino Ethyl) γ-aminopropyltrie Xisilane, N-β (aminoethyl) γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl Examples include silane coupling agents such as aminosilanes such as -γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10% by weight, preferably 0.05 to 5% by weight, based on the total amount of the colorant in the coloring composition (100% by weight).

<Color filter>
Next, the color filter of the present invention will be described. A color filter comprises a filter segment formed using a coloring composition for a color filter. Examples of the color filter include those having a red filter segment, a green filter segment, and a blue filter segment. The filter segment is coated with a color filter coloring composition by a spin coat method or a die coat method, and then ultraviolet rays or the like. The active energy rays are irradiated to cure the portion that becomes the filter segment, and then developed to form on the substrate. The red filter segment therein is formed from a coloring composition or a photosensitive coloring composition containing the colorant of the present invention.

  The green filter segment can be formed using a normal green coloring composition or a green photosensitive coloring composition containing a green pigment and a pigment carrier. Examples of the green pigment include C.I. I. Pigment Green 7, 10, 36, 37, 58, etc. are used. Blue pigments such as aluminum phthalocyanine can also be used.

  Moreover, a yellow pigment can be used together with a green coloring composition or a green photosensitive coloring composition. Examples of yellow pigments that can be used in combination include C.I. I. 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, Mention may be made of yellow pigments such as 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, or 221. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.

  The blue filter segment can be formed using a normal blue coloring composition or a blue photosensitive coloring composition containing a blue pigment and a pigment carrier. Examples of blue pigments include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, etc. are used. A purple pigment can be used in combination with the blue coloring composition or the blue photosensitive coloring composition. Examples of purple pigments that can be used in combination include C.I. I. And violet pigments such as CI Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, and 50. In addition, a basic dye or a salt-forming compound of an acid dye exhibiting blue or purple can be used. When using a dye, a xanthene dye is preferable in terms of heat resistance and luminance.

(Color filter manufacturing method)
The color filter can be manufactured by a printing method or a photolithography method.
The formation of the filter segment by the printing method can be patterned simply by repeating the printing and drying of the coloring composition prepared as the printing ink. Therefore, the color filter manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. In order to perform printing, it is preferable that the ink does not dry and solidify on the printing plate or on the blanket. Control of ink fluidity on a printing press is also important, and ink viscosity can be adjusted with a dispersant or extender pigment.

  When the filter segment is formed by photolithography, the colored composition prepared as a solvent developing type or alkali developing type colored resist material is applied on a transparent substrate by spray coating, spin coating, slit coating, roll coating or the like. By a method, it applies so that a dry film thickness may be set to 0.2-5 micrometers. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern provided in contact with or non-contact with the film. Then, after immersing in a solvent or alkali developer or spraying the developer by spraying or the like to remove the uncured portion to form a desired pattern, the same operation is repeated for other colors to produce a color filter. be able to. Furthermore, in order to accelerate the polymerization of the colored resist material, heating can be performed as necessary. According to the photolithography method, a color filter with higher accuracy than the above printing method can be manufactured.

  In development, an aqueous solution such as sodium carbonate or sodium hydroxide is used as an alkali developer, and an organic alkali such as dimethylbenzylamine or triethanolamine can also be used. Moreover, an antifoamer and surfactant can also be added to a developing solution. In order to increase the UV exposure sensitivity, after coating and drying the colored resist, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or a water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Thereafter, ultraviolet exposure can also be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, or the like in addition to the above method, but the colored composition or the photosensitive colored composition of the present invention can be used in any method. The electrodeposition method is a method for producing a color filter by using a transparent conductive film formed on a substrate and forming each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. . The transfer method is a method in which a filter segment is formed in advance on the surface of a peelable transfer base sheet, and this filter segment is transferred to a desired substrate.

  A black matrix can be formed in advance before forming each color filter segment on a transparent substrate or a reflective substrate. As the black matrix, a chromium, chromium / chromium oxide multilayer film, an inorganic film such as titanium nitride, or a resin film in which a light-shielding agent is dispersed is used, but is not limited thereto. Further, a thin film transistor (TFT) may be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment may be formed. In addition, an overcoat film, a transparent conductive film, or the like is formed on the color filter of the present invention as necessary.

  Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “part” and “%” represent “part by weight” and “% by weight”, respectively, unless otherwise specified.

  The average primary particle diameter of the pigment, the pigment identification method, the weight average molecular weight (Mw) of the resin, and the acid value of the resin were determined by the following methods.

(Average primary particle diameter of pigment)
The average primary particle diameter of the pigment was measured (calculated) by the following method.
Propylene glycol monomethyl ether acetate was added to the pigment powder, a small amount of Disperbyk-161 was added as a resin-type dispersant, and dispersed for 1 minute with an ultrasonic cleaner to prepare a measurement sample. This sample was photographed with a transmission electron microscope (“JEM-1200EX” manufactured by JEOL Ltd.), and three photographs (for three fields of view) in which primary particles of 100 or more pigments can be confirmed were taken. The size of primary particles was measured. Specifically, the short axis diameter and major axis diameter of the primary particles of each pigment are measured in nm units, the average is the primary particle diameter of the pigment, and a total of 300 distributions are created in 5 nm increments. The number average particle size was calculated by approximating the median value of the increments (for example, 8 nm in the case of 6 nm or more and 10 nm or less) as the particle size of those particles and calculating based on the particle size and the number thereof.

(Pigment identification method)
For identification of the pigment constituting the colorant of the present invention, a MALDI mass spectrometer autoflex III (hereinafter referred to as TOF-MS) manufactured by Bruker Daltonics was used, and the molecular ion peak of the obtained mass spectrum was calculated. Using the 2400 CHN Element Analyzer manufactured by Perkin Elmer, the ratio of carbon, hydrogen, and nitrogen to be obtained was matched with the theoretical value.

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

(Resin acid value)
To 0.5 to 1.0 part of the resin solution, 80 parts of acetone and 10 parts of water are added and stirred to dissolve uniformly. Using a 0.1 mol / L KOH aqueous solution as a titrant, an automatic titrator (“COM- And the acid value of the resin solution was measured. Then, the acid value per solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

(Method for producing binder resin solution)
(Preparation of acrylic resin solution 1)
A reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device was charged with 196 parts of cyclohexanone, heated to 80 ° C., and purged with nitrogen in the reaction vessel. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.) 20.7 A mixture of 1.1 parts of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add methoxypropyl acetate to the previously synthesized resin solution so that the nonvolatile content is 20%. Acrylic resin solution 1 was prepared by addition. The weight average molecular weight (Mw) was 26000.

(Preparation of acrylic resin solution 2)
207 parts of cyclohexanone was charged into a reaction vessel equipped with a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer, and the temperature was raised to 80 ° C. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2′-azobis A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was further continued for 3 hours to obtain a copolymer resin solution. Next, after the nitrogen gas was stopped and stirred while injecting dry air for 1 hour with respect to the total amount of the copolymer solution obtained, the mixture was cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Karenz manufactured by Showa Denko KK). MOI) A mixture of 6.5 parts, 0.08 part dibutyltin laurate and 26 parts cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropwise addition, the reaction was further continued for 1 hour to obtain an acrylic resin solution. After cooling to room temperature, sample about 2 parts of the resin solution, heat dry at 180 ° C. for 20 minutes, measure the nonvolatile content, and add cyclohexanone to the previously synthesized resin solution so that the nonvolatile content is 20%. Thus, an acrylic resin solution 2 was prepared. The weight average molecular weight (Mw) was 18000.

(Method for producing colorant)
Specific production methods (synthesis methods) of the pigment constituting the colorant of the present invention will be specifically described below in Examples.

[Example 1]
(Production of red colorant 1 (RP-1))
Below, the specific synthesis method of the said azo pigment 1 is shown with the reaction scheme (the following reaction scheme A). Other azo pigments according to the present invention can be synthesized according to a similar scheme. In addition, the manufacturing method (synthesis method) of an azo pigment is not limited to the following method.

(1) Synthesis of azo compound a After adding 62 parts of 4-methoxy-3-amino-benzoic acid amide to 1500 parts of water, 147 parts of 35% hydrochloric acid was added and cooled to −2 to 0 ° C. After adding 104 parts of 25% aqueous sodium nitrite solution to this solution, the mixture was stirred for 30 minutes while maintaining at 0 to 5 ° C. to prepare a diazonium solution. Separately, a coupler solution consisting of 70 parts of 2,3-hydroxynaphthoic acid, 158 parts of 25% sodium hydroxide solution and 1500 parts of water was prepared. The adjusted diazonium solution and coupler solution were simultaneously added dropwise to 3000 parts of an acetic acid buffer solution having a pH of 5.4 over 10 minutes. After completion of the dropwise addition, the mixture was stirred at room temperature for 30 minutes, and further stirred while maintaining at 80 ° C. The precipitated reaction product was collected by filtration, washed with hot water, and dried to obtain 132 parts of compound (B) (yield : 98.0%).

(1) Synthesis of Azo Pigment 1 122 parts of Compound (B) and 10 parts of N, N-dimethylformamide were added to 900 parts of O-xylene, heated to 85 ° C., and 42 parts of thionyl chloride was added dropwise over 30 minutes. . After completion of the dropwise addition, the mixture was refluxed for 2 hours. The above reaction solution was added dropwise to a solution prepared by separately heating 17 parts of 1,4-phenylenediamine and 1500 parts of O-xylene at 85 ° C. over 1 hour and refluxed for 4 hours. After cooling this reaction liquid to 95 ° C, 20 parts of 28% aqueous ammonia solution and 20 parts of water were added and stirred at 95-100 ° C for 30 minutes. The precipitated reaction product was collected by filtration, and O-xylene, methanol, and After washing with hot water and drying, 99 parts of azo pigment 1 (yield: 78.9%) were obtained. From the results of mass spectrometry by TOF-MS and the results of elemental analysis, it was identified as azo pigment 1. Table 1 shows the results of elemental analysis.

  Next, 80 parts of the azo pigment 1, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 1 (RP-1) were obtained. The average primary particle size was 38 nm.

[Example 2]
<Production of Red Colorant 2 (RP-2)>
(Synthesis of Azo Pigment 2)
An azo pigment was prepared in the same manner as in Example 1 except that 21 parts of 2,5-dimethyl-1,4-phenylenediamine was used instead of 17 parts of 1,4-phenylenediamine used in Example 1. 105 parts (yield: 80.8%) of 2 was obtained. From the results of mass spectrometry by TOF-MS and the results of elemental analysis, it was identified as azo pigment 2.

  Next, 80 parts of the azo pigment 2, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 2 (RP-2) were obtained. The average primary particle size was 41 nm.

[Example 3]
<Production of Red Colorant 3 (RP-3)>
(Synthesis of Azo Pigment 3)
The same operation as in Example 1 was carried out except that 24 parts of 2-methyl-5-chloro-1,4-phenylenediamine was used instead of 17 parts of 1,4-phenylenediamine used in Example 1. 113 parts (yield: 84.9) of azo pigment 3 were obtained. From the results of mass spectrometry by TOF-MS and the results of elemental analysis, it was identified as azo pigment 3.

  Next, 80 parts of the azo pigment 3, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 3 (RP-3) were obtained. The average primary particle size was 43 nm.

[Example 4]
<Production of Red Colorant 4 (RP-4)>
(Synthesis of Azo Pigment 4)
An azo pigment was prepared in the same manner as in Example 1 except that 28 parts of 2,5-dichloro-1,4-phenylenediamine was used instead of 17 parts of 1,4-phenylenediamine used in Example 1. 121 parts (yield: 88.8%) of 4 was obtained. From the results of mass spectrometry by TOF-MS and the results of elemental analysis, it was identified as azo pigment 4.

  Next, 80 parts of the azo pigment 4, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 4 (RP-4) were obtained. The average primary particle size was 40 nm.

[Example 5]
<Production of Red Colorant 5 (RP-5)>
(Synthesis of Azo Pigment 5)
An azo pigment 5 was prepared in the same manner as in Example 1 except that 22 parts of 2-chloro-1,4-phenylenediamine was used instead of 17 parts of 1,4-phenylenediamine used in Example 1. 117 parts (yield: 89.4%) were obtained. From the result of mass spectrometry by TOF-MS and the result of elemental analysis, it was identified as azo pigment 5.

  Next, 80 parts of the azo pigment 5, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 5 (RP-5) were obtained. The average primary particle size was 37 nm.

[Example 6]
<Production of Red Colorant 6 (RP-6)>
(Synthesis of Azo Pigment 6)
The same operation as in Example 1 was carried out except that 27 parts of 2-chloro-5-methoxy-1,4-phenylenediamine was used instead of 17 parts of 1,4-phenylenediamine used in Example 1. 115 parts (yield: 84.8%) of azo pigment 6 were obtained. From the results of mass spectrometry by TOF-MS and the results of elemental analysis, it was identified as azo pigment 6.

  Next, 80 parts of the azo pigment 6, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 6 (RP-6) were obtained. The average primary particle size was 36 nm.

[Example 7]
<Production of Red Colorant 7 (RP-7)>
(Synthesis of Azo Pigment 7)
An azo pigment was prepared in the same manner as in Example 1 except that 26 parts of 2,5-dimethoxy-1,4-phenylenediamine was used instead of 17 parts of 1,4-phenylenediamine used in Example 1. 107 parts (yield: 79.4%) of 7 was obtained. From the results of mass spectrometry by TOF-MS and the results of elemental analysis, it was identified as azo pigment 7.

  Next, 80 parts of the azo pigment 7, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 7 (RP-7) were obtained. The average primary particle size was 42 nm.

[Example 8]
<Production of Red Colorant 8 (RP-8)>
(Synthesis of Azo Pigment 8)
The same operation as in Example 1 was conducted except that 33 parts of 2-chloro-5-trifluoromethyl-1,4-phenylenediamine was used instead of 17 parts of 1,4-phenylenediamine used in Example 1. As a result, 120 parts (yield: 84.8%) of azo pigment 8 were obtained. From the results of mass spectrometry by TOF-MS and the results of elemental analysis, it was identified as azo pigment 8.

  Next, 80 parts of the azo pigment 8, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 8 (RP-8) were obtained. The average primary particle size was 40 nm.

[Example 9]
<Production of Red Colorant 9 (RP-9)>
(Synthesis of Azo Pigment 9)
An azo pigment was prepared in the same manner as in Example 1 except that 28 parts of 2-trifluoromethyl-1,4-phenylenediamine was used instead of 17 parts of 1,4-phenylenediamine used in Example 1. 116 parts (yield: 85.2%) of 9 was obtained. From the results of mass spectrometry by TOF-MS and the results of elemental analysis, it was identified as azo pigment 9.

  Next, 80 parts of the azo pigment 9, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 9 (RP-9) were obtained. The average primary particle size was 35 nm.

[Example 10]
<Production of Red Colorant 10 (RP-10)>
(Synthesis of Azo Pigment 10)
An azo pigment 10 was prepared in the same manner as in Example 1 except that 24 parts of 2-nitro-1,4-phenylenediamine was used instead of 17 parts of 1,4-phenylenediamine used in Example 1. 119 parts (yield: 89.9%) were obtained. From the result of mass spectrometry by TOF-MS and the result of elemental analysis, it was identified as the azo pigment 10.

  Next, 80 parts of the azo pigment 10, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 10 (RP-10) were obtained. The average primary particle size was 39 nm.

[Example 11]
<Production of Red Colorant 11 (RP-11)>
(Synthesis of Azo Pigment 11)
The same procedure as in Example 1 was performed, except that 21 parts of 2-cyano-1,4-phenylenediamine was used instead of 17 parts of 1,4-phenylenediamine used in Example 1, and azo pigment 11 was obtained. 116 parts (yield: 89.7%) were obtained. From the results of mass spectrometry by TOF-MS and the results of elemental analysis, it was identified as azo pigment 11.

  Next, 80 parts of the azo pigment 11, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 11 (RP-11) were obtained. The average primary particle size was 41 nm.

[Example 12]
<Production of red colorant 12 (RP-12)>
(Synthesis of azo pigment 12)
Instead of 62 parts 4-methoxy-3-amino-benzoic acid amide used in Example 1, 90 parts 4-methoxy-3-amino-benzoic acid anilide, 17 parts 1,4-phenylenediamine instead of 2 parts Except for using 22 parts of 1,5-dimethoxy-1,4-phenylenediamine, the same operation as in Example 1 was performed to obtain 105 parts of azo pigment 12 (yield: 79.3%). From the results of mass spectrometry by TOF-MS and the results of elemental analysis, the azo pigment 12 was identified.

  Next, 80 parts of the azo pigment 12, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 12 (RP-12) were obtained. The average primary particle size was 36 nm.

[Example 13]
<Production of Red Colorant 13 (RP-13)>
(Synthesis of azo pigment 13)
Instead of 62 parts 4-methoxy-3-amino-benzoic acid amide used in Example 1, 90 parts 4-methoxy-3-amino-benzoic acid anilide, 17 parts 1,4-phenylenediamine instead of 2 parts Except for using 23 parts of 1,5-dichloro-1,4-phenylenediamine, the same operation as in Example 1 was carried out to obtain 119 parts of azo pigment 13 (yield: 89.1%). From the results of mass spectrometry by TOF-MS and the results of elemental analysis, the azo pigment 13 was identified.

  Next, 80 parts of the azo pigment 13, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 13 (RP-13) were obtained. The average primary particle size was 39 nm.

[Example 14]
<Production of Red Colorant 14 (RP-14)>
(Synthesis of azo pigment 14)
Instead of 62 parts 4-methoxy-3-amino-benzoic acid amide used in Example 1, 90 parts 4-methoxy-3-amino-benzoic acid anilide, 17 parts 1,4-phenylenediamine instead of 2 parts Except for using 20 parts of -chloro-5-methyl-1,4-phenylenediamine, the same operation as in Example 1 was carried out to obtain 111 parts of azo pigment 14 (yield: 84.8%). From the result of mass spectrometry by TOF-MS and the result of elemental analysis, it was identified as the azo pigment 14.

  Next, 80 parts of the azo pigment 14, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 14 (RP-14) were obtained. The average primary particle size was 35 nm.

[Example 15]
<Production of Red Colorant 15 (RP-15)>
(Synthesis of azo pigment 15)
Instead of 62 parts 4-methoxy-3-amino-benzoic acid amide used in Example 1, 90 parts 4-methoxy-3-amino-benzoic acid anilide, 17 parts 1,4-phenylenediamine instead of 2 parts Except for using 23 parts of -chloro-5-methoxy-1,4-phenylenediamine, the same operation as in Example 1 was carried out to obtain 113 parts of azo pigment 15 (yield: 85.0%). From the result of mass spectrometry by TOF-MS and the result of elemental analysis, it was identified as azo pigment 15.

Next, 80 parts of the azo pigment 1, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 15 (RP-15) were obtained. The average primary particle size was 38 nm.
[Example 16]
<Production of Red Colorant 16 (RP-16)>
(Synthesis of azo pigment 16)
Instead of 62 parts 4-methoxy-3-amino-benzoic acid amide used in Example 1, 90 parts 4-methoxy-3-amino-benzoic acid anilide, 17 parts 1,4-phenylenediamine instead of 2 parts Except for using 28 parts of -chloro-5-trifluoromethyl-1,4-phenylenediamine, the same operation as in Example 1 was performed to obtain 117 parts of azo pigment 16 (yield: 84.8%). . From the result of mass spectrometry by TOF-MS and the result of elemental analysis, it was identified as azo pigment 16.

  Next, 80 parts of the azo pigment 16, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 16 (RP-16) were obtained. The average primary particle size was 40 nm.

[Example 17]
<Production of Red Colorant 17 (RP-17)>
(Synthesis of Azo Pigment 17)
Instead of 62 parts of 4-methoxy-3-amino-benzoic acid amide used in Example 1, 103 parts of 4-methoxy-3-amino-benzoic acid- (3′-chloro) -anilide, 1,4-phenylene The same operation as in Example 1 was carried out except that 22 parts of 2,5-dichloro-1,4-phenylenediamine was used instead of 17 parts of diamine, and 118 parts of azo pigment 17 (yield: 89.0). %)Obtained. From the result of the mass spectrometry by TOF-MS and the result of the elemental analysis, it was identified as the azo pigment 17.

  Next, 80 parts of the azo pigment 17, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 17 (RP-17) were obtained. The average primary particle size was 41 nm.

[Example 18]
<Production of Red Colorant 18 (RP-18)>
(Synthesis of azo pigment 18)
Instead of 62 parts of 4-methoxy-3-amino-benzoic acid amide used in Example 1, 115 parts of 4-methoxy-3-amino-benzoic acid- (3′-trifluoromethyl) -anilide, 1,4 -Instead of 17 parts of phenylenediamine, the same operation as in Example 1 was carried out except that 20 parts of 2,5-dichloro-1,4-phenylenediamine was used, and 117 parts of azo pigment 18 (yield: 88). .8) Obtained. From the result of mass spectrometry by TOF-MS and the result of elemental analysis, it was identified as the azo pigment 18.

  Next, 80 parts of the azo pigment 18, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 18 (RP-18) were obtained. The average primary particle size was 44 nm.

[Example 19]
<Production of Red Colorant 19 (RP-19)>
(Synthesis of Azo Pigment 19)
Instead of 62 parts of 4-methoxy-3-amino-benzoic acid amide used in Example 1, 4-methoxy-3-amino-benzoic acid- (2′-chloro-5′-trifluoromethyl) -anilide 128 In the same manner as in Example 1 except that 19 parts of 2,5-dichloro-1,4-phenylenediamine was used instead of 17 parts of 1,4-phenylenediamine, and 117 parts of azo pigment 19 was obtained. (Yield: 89.2%) was obtained. From the results of mass spectrometry by TOF-MS and the results of elemental analysis, the azo pigment 19 was identified.

  Next, 80 parts of the azo pigment 19, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling treatment. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 19 (RP-19) were obtained. The average primary particle size was 38 nm.

[Example 20]
<Production of Red Colorant 20 (RP-20)>
(Synthesis of Azo Pigment 20)
Instead of 62 parts of 4-methoxy-3-amino-benzoic acid amide used in Example 1, 117 parts of 4-methoxy-3-amino-benzoic acid- (2′-methyl-5′-carbomethoxy) -anilide In the same manner as in Example 1 except that 20 parts of 2,5-dichloro-1,4-phenylenediamine was used instead of 17 parts of 1,4-phenylenediamine, 117 parts of azo pigment 20 ( (Yield: 88.8%). From the results of mass spectrometry by TOF-MS and the results of elemental analysis, the azo pigment 20 was identified.

  Next, 80 parts of the azo pigment 20, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 20 (RP-20) were obtained. The average primary particle size was 43 nm.

[Example 21]
<Production of Red Colorant 21 (RP-21)>
(Synthesis of Azo Pigment 21)
Instead of 62 parts of 4-methoxy-3-amino-benzoic acid amide used in Example 1, 111 parts of pigment (4-1), 17 parts of 1,4-phenylenediamine, 2,5-dichloro- The same operation as in Example 1 was carried out except that 21 parts of 1,4-phenylenediamine was used to obtain 118 parts of azo pigment 21 (yield: 89.3%). From the result of mass spectrometry by TOF-MS and the result of elemental analysis, it was identified as the azo pigment 21.

Pigment (4-1)

  Next, 80 parts of the azo pigment 21, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 21 (RP-21) were obtained. The average primary particle size was 42 nm.

[Example 22]
<Production of red colorant 22 (RP-22)>
(Synthesis of Azo Pigment 22)
Instead of 62 parts of 4-methoxy-3-amino-benzoic acid amide used in Example 1, 67 parts of 4-methoxy-3-amino-benzoic acid methylamide and 17 parts of 1,4-phenylenediamine 2 Except for using 27 parts of 1,5-dichloro-1,4-phenylenediamine, the same operation as in Example 1 was performed to obtain 121 parts of azo pigment 22 (yield: 89.2%). From the results of mass spectrometry by TOF-MS and the results of elemental analysis, the azo pigment 22 was identified.

  Next, 80 parts of the azo pigment 22, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 22 (RP-22) were obtained. The average primary particle size was 41 nm.

[Example 23]
<Production of Red Colorant 23 (RP-23)>
(Synthesis of Azo Pigment 23)
Instead of 62 parts 4-methoxy-3-amino-benzoic acid amide used in Example 1, 83 parts 4-methoxy-3-amino-benzoic acid butyramide and 17 parts 1,4-phenylenediamine 2 Except for using 24 parts of 1,5-dichloro-1,4-phenylenediamine, the same operation as in Example 1 was carried out to obtain 119 parts of azo pigment 23 (yield: 88.7%). From the result of mass spectrometry by TOF-MS and the result of elemental analysis, it was identified as the azo pigment 23.

  Next, 80 parts of the azo pigment 23, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 23 (RP-23) were obtained. The average primary particle size was 39 nm.

[Example 24]
<Production of Red Colorant 24 (RP-24)>
(Synthesis of Azo Pigment 24)
Instead of 62 parts of 4-methoxy-3-amino-benzoic acid amide used in Example 1, 83 parts of 4-methoxy-3-amino-benzoic acid diethylamide, 17 parts of 1,4-phenylenediamine, 2 parts Except for using 24 parts of 1,5-dichloro-1,4-phenylenediamine, the same operation as in Example 1 was performed to obtain 120 parts of azo pigment 24 (yield: 89.4%). From the results of mass spectrometry by TOF-MS and the results of elemental analysis, the azo pigment 24 was identified.

  Next, 80 parts of the azo pigment 24, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 24 (RP-24) were obtained. The average primary particle size was 42 nm.

[Example 25]
<Production of Red Colorant 25 (RP-25)>
(Synthesis of Azo Pigment 25)
Instead of 62 parts of 4-methoxy-3-amino-benzoic acid amide used in Example 1, 103 parts of 4-methoxy-3-amino-benzoic acid dibutylamide and 17 parts of 1,4-phenylenediamine, The same operation as in Example 1 was carried out except that 21 parts of 2,5-dichloro-1,4-phenylenediamine was used to obtain 118 parts of azo pigment 25 (yield: 89.0%). From the results of mass spectrometry by TOF-MS and the results of elemental analysis, the azo pigment 25 was identified.

  Next, 80 parts of the azo pigment 25, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 25 (RP-25) were obtained. The average primary particle size was 43 nm.

[Example 26]
<Production of Red Colorant 26 (RP-26)>
(Synthesis of Azo Pigment 26)
Instead of 62 parts of 4-methoxy-3-amino-benzoic acid amide used in Example 1, 77 parts of 4-butoxy-3-amino-benzoic acid amide, 17 parts of 1,4-phenylenediamine, 2 parts Except for using 25 parts of 1,5-dichloro-1,4-phenylenediamine, the same operation as in Example 1 was performed to obtain 120 parts of azo pigment 26 (yield: 89.1%). From the results of mass spectrometry by TOF-MS and the results of elemental analysis, the azo pigment 26 was identified.

  Next, 80 parts of the azo pigment 26, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 26 (RP-26) were obtained. The average primary particle size was 41 nm.

[Example 27]
<Production of Red Colorant 27 (RP-27)>
(Synthesis of a mixture of azo pigment 4 and azo pigment 13)
Instead of 62 parts of 4-methoxy-3-amino-benzoic acid amide used in Example 1, 31 parts of 4-methoxy-3-amino-benzoic acid amide and 45 parts of 4-methoxy-3-amino-benzoic acid anilide In the same manner as in Example 1 except that 25 parts of 2,5-dichloro-1,4-phenylenediamine was used instead of 17 parts of 1,4-phenylenediamine, azo pigment 4 and azo pigment 13 117 parts (yield: 86.9%) was obtained. From the result of mass spectrometry by TOF-MS, it was identified that it was a mixture of the azo pigment 4 and the azo pigment 13.

  Next, 80 parts of the mixture of the azo pigment 4 and the azo pigment 13, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. Salt milling was performed. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 27 (RP-27) were obtained. The average primary particle size was 38 nm.

[Example 28]
<Production of Red Colorant 28 (RP-28)>
(Synthesis of a mixture of the azo pigment 13 and the azo pigment 15)
Instead of 62 parts 4-methoxy-3-amino-benzoic acid amide used in Example 1, 90 parts 4-methoxy-3-amino-benzoic acid anilide, 17 parts 1,4-phenylenediamine instead of 2 parts , Except that 12 parts of 2,5-dichloro-1,4-phenylenediamine and 11 parts of 2-chloro-5-methoxy-1,4-phenylenediamine were used. 116 parts (yield: 87.0%) of a mixture with the azo pigment 15 were obtained. From the result of the mass spectrometry result by TOF-MS, it was identified that it was a mixture of the azo pigment 13 and the azo pigment 15.

  Next, 80 parts of the mixture of the azo pigment 13 and the azo pigment 15, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. Salt milling was performed. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 78 parts of red colorant 28 (RP-28) were obtained. The average primary particle size was 35 nm.

[Example 29]
<Production of Red Colorant 29 (RP-29)>
Instead of 80 parts of the azo pigment 1 used in Example 1, 75 parts of the azo pigment 1 and 5 parts of the dye derivative represented by the formula (10-3) were used. And 78 parts of red colorant 29 (RP-29) were obtained. The average primary particle size was 31 nm.

[Example 30]
<Production of Red Colorant 30 (RP-30)>
Instead of 80 parts of the azo pigment 1 used in Example 1, 75 parts of the azo pigment 1 and 5 parts of the dye derivative represented by the formula (11-9) were used. And 78 parts of red colorant 30 (RP-30) were obtained. The average primary particle size was 30 nm.

[Example 31]
<Production of Red Colorant 31 (RP-31)>
Instead of 80 parts of the azo pigment 1 used in Example 1, 75 parts of the azo pigment 1 and 5 parts of the dye derivative represented by the formula (14-2) were used. And 78 parts of red colorant 31 (RP-31) were obtained. The average primary particle size was 33 nm.

[Example 32]
<Production of Red Colorant 32 (RP-32)>
Instead of 80 parts of the azo pigment 1 used in Example 1, 75 parts of the azo pigment 1 and 5 parts of the dye derivative represented by the formula (15-5) were used. And 78 parts of red colorant 32 (RP-32) were obtained. The average primary particle size was 29 nm.

[Example 33]
<Production of Red Colorant 33 (RP-33)>
Instead of 80 parts of the azo pigment 1 used in Example 1, 75 parts of the azo pigment 1 and 5 parts of the dye derivative represented by the formula (16-8) were used. And 78 parts of red colorant 33 (RP-33) were obtained. The average primary particle size was 27 nm.

[Example 34]
<Production of Red Colorant 34 (RP-34)>
Instead of 80 parts of the azo pigment 1 used in Example 1, 75 parts of the azo pigment 1 and 5 parts of the dye derivative represented by the formula (18-4) were used, and the same operation as in Example 1 was performed. And 78 parts of red colorant 34 (RP-34) were obtained. The average primary particle size was 29 nm.

[Example 35]
<Production of Red Colorant 35 (RP-35)>
80 parts of the azo pigment 1 obtained in Example 1 was added to 1200 parts of concentrated sulfuric acid, and the mixture was stirred at 40 ° C. for 3 hours, and then this sulfuric acid solution was poured into 24000 parts of cold water at 3 ° C. The produced precipitate was filtered, washed with water, and dried overnight at 80 ° C. to obtain 78 parts of red colorant 35 (RP-35). The average primary particle size was 37 nm.

(Manufacturing method of other red colorants)
[Production Example 1]
(Production of red colorant 36 (RP-36))
Commercially available C.I. I. 100 parts of Pigment Red 254 (PR254) ("Irgafoa Red B-CF" manufactured by Ciba Specialty Chemicals), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) at 60 ° C. And kneaded for 6 hours and subjected to salt milling. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red colorant 36 (RP-36) were obtained. The average primary particle size was 33 nm.

[Production Example 2]
(Production of red colorant 37 (RP-37))
C. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals) I. Pigment Red 177 (PR177) (“CROMOPHTAL RED A2B” manufactured by BASF) was used in the same manner as in the production of red colorant 36 (RP-36), and 97 parts of red colorant 37 (RP-37) was used. Obtained. The average primary particle size was 37 nm.

[Production Example 3]
(Production of red colorant 38 (RP-38))
C. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals) I. Pigment Red 242 (PR242) (Clariant's SandorinScallet 4RF) was used except that the red colorant 36 (RP-36) was produced, and 98 parts of a red colorant 38 (RP-38) was obtained. The average primary particle size was 39 nm.

[Production Example 4]
(Production of red colorant 39 (RP-39))
C. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals) I. Pigment Red 176 (PR176) (“Novoperm Carmine HF3C” manufactured by Clariant) was used in the same manner as in the production of red colorant 36 (RP-36), and 98 parts of red colorant 39 (RP-39) was used. Obtained. The average primary particle size was 35 nm.

[Production Example 5]
(Production of red colorant 40 (RP-40))
C. I. Pigment Red 254 (“Irgafore Red B-CF” manufactured by Ciba Specialty Chemicals) I. Pigment Orange 38 (PO38) (“Novoperm Red HF part” manufactured by Clariant) was performed in the same manner as in the production of red colorant 36 (RP-36), and 97 parts of red colorant 40 (RP-40). Got. The average primary particle size was 39 nm.

[Production Example 6]
(Production of red colorant 41 (RP-41))
(Brominated diketopyrrolopyrrole pigment)
To a stainless steel reaction vessel equipped with a reflux tube, 200 parts of tert-amyl alcohol dehydrated with molecular sieves and 140 parts of sodium-tert-amyl alkoxide are added in a nitrogen atmosphere and heated to 100 ° C. with stirring to obtain an alcoholate solution. Prepared. On the other hand, 88 parts of diisopropyl succinate and 153.6 parts of 4-bromobenzonitrile were added to a glass flask and dissolved by heating to 90 ° C. with stirring to prepare a solution of these mixtures. The heated solution of the mixture was slowly dropped into the alcoholate solution heated to 100 ° C. at a constant rate over 2 hours with vigorous stirring. After completion of the dropwise addition, heating and stirring were continued at 90 ° C. for 2 hours to obtain an alkali metal salt of a diketopyrrolopyrrole pigment. Furthermore, 600 parts of methanol, 600 parts of water and 304 parts of acetic acid were added to a reaction vessel with a glass jacket, and cooled to -10 ° C. While cooling this mixture with a high-speed stirring disperser, rotating a shear disk having a diameter of 8 cm at 4000 rpm, the alkali metal salt of the diketopyrrolopyrrole pigment obtained above was cooled to 75 ° C. The solution was added in small portions. At this time, the rate of addition of the alkali metal salt of the diketopyrrolopyrrole pigment at 75 ° C. while cooling so that the temperature of the mixture consisting of methanol, acetic acid and water is always kept at −5 ° C. or lower. Was added in small portions over approximately 120 minutes. After addition of the alkali metal salt, red crystals were precipitated to form a red suspension. Subsequently, the obtained red suspension was washed with an ultrafiltration device at 5 ° C. and then filtered to obtain a red paste. This paste was re-dispersed in 3500 parts of methanol cooled to 0 ° C. to make a suspension with a methanol concentration of about 90%, and stirred at 5 ° C. for 3 hours to perform particle sizing and washing with crystal transition. Subsequently, the diketopyrrolopyrrole pigment aqueous paste obtained by filtration with an ultrafilter was dried at 80 ° C. for 24 hours and pulverized to obtain 150.8 parts of a brominated diketopyrrolopyrrole pigment. Got.

  100 parts of the brominated diketopyrrolopyrrole pigment obtained above, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and subjected to a salt milling treatment. did. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while being heated to 70 ° C., made into a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. overnight. 98 parts of red colorant 41 (RP-41) were obtained. The average primary particle size was 45 nm.

(Method for producing colored composition)
[Example 36]
(Preparation of colored composition 1 (RM-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0.0 micrometer filter, and the coloring composition 1 (RM-1) was produced.
Red colorant 1 (RP-1) 10.0 parts Resin type dispersant ("PB821" manufactured by Ajinomoto Fine Techno Co., Ltd.) 3.0 parts Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

[Examples 37 to 70, Comparative Examples 1 to 3]
(Preparation of colored compositions 2 to 38 (RM-2 to 38))
Coloring compositions 2 to 38 (RM-2 to 38) are the same as coloring composition 1 (RM-1) except that red coloring agent 1 (RP-1) is changed to the red coloring agent described in Table 3. ) Was produced.

(Evaluation of coloring composition)
The obtained colored composition and the coating film produced using it were evaluated for heat resistance, light resistance and foreign matter evaluation by the following methods.

(Heat resistance evaluation)
The coloring composition was applied on a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater so that the dry film thickness was 2.0 μm, then dried at 70 ° C. for 20 minutes, and then 230 ° C. The coating film substrate (one aspect of the color filter) was produced by heating and cooling for 60 minutes. The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film with a C light source was measured with a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). And measured. Further, as a heat resistance test, the sample was heated at 250 ° C. for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) with a C light source was measured. The color difference ΔEab * was determined and evaluated in the following four stages.

ΔEab * = √ ((L * (2)-L * (1)) 2+ (a * (2)-a * (1)) 2+ (b * (2)-b * (1)) 2)

A: ΔEab * is less than 1.0 (very good)
○: ΔEab * is 1.0 or more and less than 2.5 (good)
Δ: ΔEab * is 2.5 or more and less than 5.0 (defect)
×: ΔEab * is 5.0 or more (very poor)

(Light resistance evaluation)
A coated substrate is prepared in the same manner as in the heat resistance evaluation, and the chromaticity ([L * (1), a * (1), b * (1)]) with a C light source is measured with a microspectrophotometer ( Measurement was performed using “OSP-SP100” manufactured by Olympus Optical Co., Ltd. Subsequently, an ultraviolet cut filter (“COLORED OPTICAL part LASS L38” manufactured by Hoya Co., Ltd.) was applied on the substrate, and irradiated with ultraviolet rays for 100 hours using a 470 W / m ² xenon lamp, and then the chromaticity ( [L * (2), a * (2), b * (2)]) were measured, and the color difference ΔEab * was determined by the above formula and evaluated according to the same criteria as heat resistance.

(Coating foreign material evaluation)
The coloring composition was applied onto a glass substrate of 100 mm × 100 mm and 1.1 mm thickness using a spin coater so that the dry film thickness was 2.0 μm, then dried at 70 ° C. for 20 minutes, and then 230 A coating film substrate was prepared by heating and cooling at 60 ° C. for 60 minutes. The evaluation was performed using a Olympus system metal microscope “BX60”). The magnification was 500 times, and the number of particles that were observable in arbitrary 5 fields of view through transmission was counted. Evaluation was made in the following four stages.

A: Less than 5 foreign objects (very good)
○: The number of foreign matters is 5 or more and less than 10 (good)
Δ: The number of foreign matters is 10 or more and less than 60 (defects)
×: The number of foreign matters is 60 or more (very bad)

(Storage stability test method)
The viscosity at 25 ° C. of the colored composition was measured at a rotation speed of 20 rpm using an E-type viscometer (TUE-20L type manufactured by Toki Sangyo Co., Ltd.). The viscosity change rate was calculated from the initial viscosity on the day of preparation of the colored composition and the viscosity measured after storage for 7 days in a thermostatic chamber at 40 ° C., and the storage stability was evaluated according to the following criteria.

◎: Less than 10% (very good)
○: 10% or more, less than 20% (good)
Δ: 20% or more, less than 50% (defect)
×: 50% or more (very bad)

  As shown in Table 3, the coloring composition using the colorant of the present invention had good results in the heat resistance, light resistance, coating foreign matter, and storage stability of the coating film.

(Preparation method of photosensitive coloring composition)
The coloring composition used for preparation of the photosensitive coloring composition was prepared.

(Preparation of colored composition 39 (RM-39))
A mixture having the following composition was stirred and mixed so as to be uniform, and then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm. It filtered with a 0.0 micrometer filter and the coloring composition 39 (RM-39) was produced.
Red colorant 36 (RP-36) 10.0 parts Resin type dispersant ("PB821" manufactured by Ajinomoto Fine Techno Co.) 3.0 parts Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of colored composition 40 (RM-40))
A colored composition 40 (RM-40) was produced in the same manner as the colored composition 39 (RM-39) except that the red colorant 36 (RP-36) was changed to the red colorant 38 (RP-38).

(Preparation of colored composition 41 (RM-41))
A colored composition 41 (RM-41) was produced in the same manner as the colored composition 39 (RM-39) except that the red colorant 36 (RP-36) was changed to the red colorant 41 (RP-41).

[Example 71]
(Preparation of photosensitive coloring composition 1 (RR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare photosensitive coloring composition 1 (RR-1).
Coloring composition 1 (RM-1) 20.5 parts Coloring composition 5 (RM-13) 22.5 parts Acrylic resin solution 2 8.2 parts Photopolymerizable monomer ("Aronix M402" manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator ("Irgacure 907" manufactured by Ciba Japan) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts Propylene glycol monomethyl ether acetate 43 .6 parts

[Examples 72 to 114, Comparative Examples 4 to 11]
(Photosensitive coloring composition 2 to 52 (RR-2 to 52))
The coloring composition 1 (RM-1) and the coloring composition 13 (RM-13) were combined with the coloring composition shown in Table 4 and x = 0.640, y = 0 with a C light source when the coating film was evaluated. .Sensitive coloring compositions 2 to 52 (RR-2 to 52) were carried out in the same manner as in Example 71 except that the ratio was changed to a ratio suitable for the chromaticity of 330 (a ratio within the total amount of 43 parts of the coloring composition). Obtained.

(Evaluation of coating film of photosensitive coloring composition)
Evaluation of the brightness | luminance (color characteristic) of the red coating film produced using the obtained photosensitive coloring compositions 1-52 (RR-1 to 52) was performed by the following method. Table 4 shows the evaluation results.

(Luminance evaluation)
The photosensitive coloring composition is applied onto a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, then dried at 70 ° C. for 20 minutes, and an integrated light quantity of 150 mJ is used using an ultrahigh pressure mercury lamp. UV exposure was performed at / cm ² and development was performed with an alkaline developer at 23 ° C. to obtain a coated substrate. Next, after heating at 230 ° C. for 60 minutes and allowing to cool, the luminance Y (C) of the obtained coating film substrate was measured using a microspectrophotometer (“OSP-SP100” manufactured by Olympus Optical Co., Ltd.). The prepared coated substrate was adjusted to chromaticity of x = 0.640 and y = 0.330 with a C light source after heat treatment at 230 ° C. The alkali developer is composed of 8.0% by mass of sodium carbonate 1.5% by mass, sodium hydrogen carbonate 0.5% by mass, an anionic surfactant (“PERILEX NBL” manufactured by Kao Corporation) and 90% by mass of water. Was used. Luminance Y (C) indicates that the higher the numerical value, the better, and if it is 0.1 point or more, it can be said that there is a clear difference.

  From the results in Table 4, it was revealed that the examples using the colorant of the present invention were excellent in luminance in forming color filters. In particular, C.I. conventionally used as a bluish pigment. I. Pigment red 177 and C.I. I. By using it instead of Pigment Red 176, the effect of improving the brightness was confirmed.

(Production of color filter)
The green photosensitive coloring composition and the blue photosensitive coloring composition used for preparation of a color filter were produced. In addition, about the red, the photosensitive coloring composition 1 (RR-1) of this invention was used.

(Preparation of green coloring composition 1 (GM-1))
A mixture having the composition shown below was stirred and mixed uniformly, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The green colored composition 1 (GM-1) was produced by filtering with a filter.
Green pigment (CI Pigment Green 36) 6.8 parts Yellow pigment (CI Pigment Yellow 150) 5.2 parts Resin-type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin Solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of green photosensitive coloring composition 1 (GR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare green photosensitive coloring composition 1 (GR-1).
Green coloring composition 1 (GM-1) 42.0 parts Acrylic resin solution 2 13.2 parts Photopolymerizable monomer (“Aronix M402” manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Ciba Japan) "Irgacure 907" manufactured by the company) 2.0 parts Sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 39.6 parts ethylene glycol monomethyl ether acetate

(Preparation of blue coloring composition 1 (BM-1))
The mixture having the composition shown below was stirred and mixed uniformly, and dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) for 5 hours using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The blue colored composition 1 (BM-1) was produced by filtering with a filter.
Blue pigment (CI Pigment Blue 15: 6) 7.2 parts Purple Pigment (CI Pigment Violet 23) 4.8 parts Resin type dispersant ("EFKA4300" manufactured by Ciba Japan) 1.0 part Acrylic resin solution 1 35.0 parts Propylene glycol monomethyl ether acetate 52.0 parts

(Preparation of blue photosensitive coloring composition 1 (BR-1))
A mixture having the following composition was stirred and mixed so as to be uniform, and then filtered through a 1 μm filter to prepare a blue photosensitive coloring composition 1 (BR-1).
Blue coloring composition 1 (BM-1) 34.0 parts Acrylic resin solution 2 15.2 parts Photopolymerizable monomer (“Aronix M400” manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (Ciba Japan) “Irgacure 907” manufactured by the company) 2.0 parts Sensitizer (“EAB-F” manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts 45.1 parts ethylene glycol monomethyl ether acetate

  A black matrix was patterned on a glass substrate, and the photosensitive coloring composition 1 (RR-1) of the present invention was applied onto the substrate with a spin coater to form a colored film. The coating was irradiated with 300 mJ / cm 2 of ultraviolet rays through a photomask using an ultrahigh pressure mercury lamp. Next, spray development was performed with an alkaline developer composed of a 0.2% by weight aqueous sodium carbonate solution to remove unexposed portions, followed by washing with ion-exchanged water. The substrate was heated at 230 ° C. for 20 minutes to obtain a red filter segment. Formed. The formed red filter segment was x = 0.640 and y = 0.330 with a C light source. By the same method, green photosensitive coloring composition 1 (part R-1) x = 0.300, y = 0.600, blue photosensitive coloring composition 1 (BR-1) x = 0.150, A color filter was obtained by forming a green filter segment and a blue filter segment so that y = 0.060.

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

Claims (6)

A color filter colorant comprising an azo pigment represented by the following general formula (1).
General formula (1)

[In General Formula (1), R _a and R _b each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, or a phenyl group which may have a substituent. R _c represents an alkyl group having 1 to 4 carbon atoms. X and Y each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, or a trifluoromethyl group. ]   Furthermore, the coloring agent for color filters of Claim 1 containing a pigment derivative.   A color filter coloring composition comprising at least a colorant and a binder resin, wherein the colorant is the color filter colorant according to claim 1 or 2.   Furthermore, C.I. I. Pigment red 254, C.I. I. C. I. The coloring composition for a color filter according to claim 3, comprising Pigment Red 242 and / or a brominated diketopyrrolopyrrole pigment.   Furthermore, the coloring composition for color filters of Claim 4 formed by containing a photopolymerizable monomer.   A color filter comprising a filter segment formed from the colored composition for color filter according to claim 4 or 5 on a substrate.