JP6108231B2 - Red coloring composition for color filter and color filter - Google Patents

Description

  The present invention relates to a color liquid crystal display device, a color composition for a color filter used for producing a color filter used for a color image pickup tube element, and the like, and a color filter including a filter segment formed using the same. It is.

  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 devices include an in-plane switching (IPS) method in which a pair of electrodes is provided on one substrate and electrolysis is applied in a direction parallel to the substrate, negative dielectric anisotropy Vertical alignment (VA) method for vertically aligning nematic liquid crystal with optical properties, and Optical Convencence Bend (OCB) method in which the optical axes of uniaxial retardation films are orthogonal to each other to perform optical compensation Etc., and each has been put to practical use.

  A liquid crystal display device is capable of color display by providing a color filter between two polarizing plates, and has recently been used in televisions, personal computer monitors, and the like. Increasing demands are being made.

  A color filter is a surface of a transparent substrate such as glass, in which two or more kinds of fine band (striped) filter segments of different hues are arranged in parallel or crossing each other, or 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.

  Generally, in a color liquid crystal display device, a transparent electrode for driving a liquid crystal is formed on a color filter by vapor deposition or sputtering, and an alignment film for aligning the liquid crystal in a certain direction is further formed thereon. Yes. In order to sufficiently obtain the performance of these transparent electrodes and alignment films, the formation thereof must generally be performed at a high temperature of 200 ° C. or higher, preferably 230 ° C. or higher. For this reason, at present, as a method for producing a color filter, a method called a pigment dispersion method using a pigment having excellent light resistance and heat resistance as a colorant is mainly used.

  In general, two or more kinds of pigments are used in combination in the red filter segment, which is one of the three primary colors (red, green, blue; RGB) of the color filter substrate. I. Pigment red 254 and C.I. I. Pigment Red 177 is also a yellow pigment for toning. I. Pigment yellow 150, C.I. I. Pigment yellow 138, or C.I. I. Pigment Yellow 139 or the like is used.

  Here, C.I. I. Pigment Red 254 is a pigment that is particularly excellent in luminance when made into a colored composition. Further, since the coloring power is high, it is advantageous when adjusting the chromaticity and film thickness of the color filter. However, C.I. I. Pigment Red 254 has a problem in heat resistance when used in a refined form, and has a disadvantage that the contrast ratio is lowered when a refined product is used as a colored coating film.

  As a method for obtaining a color filter having a high contrast ratio, C.I. I. Pigment Red 254, C.I. I. A technique of adding Pigment Red 177 to produce a colored composition is used. However, C.I. I. Pigment Red 177 itself has low luminance and coloring power, so it cannot be used at a high content rate. I. Pigment Red 254 and C.I. I. When Pigment Red 177 is contained, the luminance, coloring power, and contrast are low in terms of arithmetic average, and as long as the combination of the red pigment and the yellow pigment that are conventionally used can be used, the high contrast ratio and the high brightness are the limits. This is the current situation.

  In Patent Documents 1 to 3, in order to further improve the brightness 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 the brightness is not sufficient, and further improvement has been demanded.

  Naphthol azo pigments have C.I. affinity for the solvent itself and the acidity of the pigment surface. I. Pigment red 254 and C.I. I. Since it is different from CI Pigment Red 177 and the like, it has been impossible to obtain a colored composition that is excellent in dispersibility, fluidity, storage stability, and has high brightness and contrast ratio.

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

  The present invention is a stable color filter coloring composition having high brightness and contrast ratio and excellent fluidity, and has good color characteristics and heat resistance formed using the color filter coloring composition. It is to provide an excellent color filter.

  As a result of intensive studies to solve the above problems, the present inventors include a naphthol azo pigment (a1) represented by the general formula (1) and a resin-type dispersant having a basic substituent. It has been found that the above-mentioned problems can be solved by a coloring composition.

That is, the present invention relates to a coloring composition containing a colorant (a), a resin (b), a resin-type dispersant (c), and a solvent (d), wherein the colorant (a) A red coloring composition for a color filter, comprising a naphtholazo pigment (a1) represented by formula (1), wherein the resinous dispersant (c) is a resinous dispersant having a basic substituent About.


[In General Formula (1), A represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent.
R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ , or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , or an _-SO 2 ^{NHR 12.} R ^{7 to} R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
However, it excludes when A and R ^{2 to} R ⁶ are a hydrogen atom and R ¹ is a halogen atom. ]

The present invention also relates to the above naphthol azo pigment, wherein A is a phenyl group which may have a substituent.
The present invention also relates to the red coloring composition for a color filter, wherein the resin type dispersant (c) has a basic substituent containing a nitrogen atom.
The present invention further includes a dye derivative (e), wherein the dye derivative (e) includes a pigment derivative having an acidic substituent, a β-naphthol derivative having an acidic substituent, and a triazine derivative having an acidic substituent. It contains the pigment derivative which has the at least 1 sort (s) of acidic substituent selected from the group which consists of the said red coloring composition for color filters characterized by the above-mentioned.
In the present invention, the colorant (a) further comprises C.I. I. Pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment yellow 139 and C.I. I. The present invention relates to the red coloring composition for a color filter, comprising at least one pigment selected from the group consisting of CI Pigment Yellow 150.
The present invention further relates to the red coloring composition for a color filter, further comprising a photopolymerizable monomer and / or a photopolymerization initiator.

  The present invention also relates to a color filter comprising a red filter segment formed from the red coloring composition for a color filter on a substrate.

  According to the present invention, by using the naphthol azo pigment (a1) represented by the general formula (1) and the resin-type dispersant having a basic substituent, brightness and contrast ratio are high, high fluidity, and stability. By using this composition, it becomes possible to form a color filter with good color characteristics, high brightness and high contrast ratio.

Hereinafter, the present invention will be described in detail.
The red coloring composition for a color filter of the present invention comprises a colorant (a) containing a naphthol azo pigment (a1) represented by the general formula (1), a resin (b), and a resin type dispersion having a basic substituent. It is a coloring composition containing the resin-type dispersant (c) which is a chemical agent, and a solvent (d).

<Colorant (a)>
The colorant (a) in the coloring composition for a color filter of the present invention is characterized by containing a naphthol azo pigment (a1) represented by the general formula (1).

[In General Formula (1), A represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent.
R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ , or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , or an _-SO 2 ^{NHR 12.} R ^{7 to} R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
However, it excludes when A and R ^{2 to} R ⁶ are a hydrogen atom and R ¹ is a halogen atom. ]

  In the general formula (1), in A, the “substituent” of the phenyl group which may have a substituent is a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, cyano Of an acidic group selected from a group, a trifluoromethyl group, a nitro group, a hydroxyl group, a carbamoyl group, an N-substituted carbamoyl group, a sulfamoyl group, an N-substituted sulfamoyl group, a carboxyl group, a sulfo group, a carboxyl group or a sulfo group Trivalent metal salts (for example, sodium salt, potassium salt, aluminum salt, etc.) and the like can be mentioned. Therefore, specific examples of the phenyl group which may have a substituent include a phenyl group, a p-methylphenyl group, a 4-tert-butylphenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, an o-triphenyl group. Fluoromethylphenyl group, p-chlorophenyl group, p-bromophenyl group, 2,4-dichlorophenyl group, 3-carbamoylphenyl group, 2-chloro-4-carbamoylphenyl group, 2-methyl-4-carbamoylphenyl group, 2 -Methoxy-4-carbamoylphenyl group, 2-methoxy-4-methyl-3-sulfamoylphenyl group, 4-sulfophenyl group, 4-carboxyphenyl group, 2-methyl-4-sulfophenyl group, etc. However, it is not limited to these.

  In A, even if it has a substituent, the “substituent” of the heterocyclic group includes a halogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxyl group having 1 to 4 carbon atoms, a cyano group, and trifluoromethyl. Monovalent to trivalent metal salt of an acidic group selected from a group, nitro group, hydroxyl group, carbamoyl group, N-substituted carbamoyl group, sulfamoyl group, N-substituted sulfamoyl group, carboxyl group, sulfo group, carboxyl group or sulfo group (For example, sodium salt, potassium salt, aluminum salt, etc.). “Heterocycle” means an atom in which one or more heteroatoms other than carbon atoms are contained in the atoms constituting the ring system, and may be a saturated ring or an unsaturated ring. Further, it may be a single ring or a condensed ring. Therefore, the heterocyclic ring includes pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, triazine ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, pyrazole ring, oxazole ring, thiazole ring, isoxazole ring, isothiazole ring. , Triazole ring, thiadiazole ring, oxadiazole ring, quinoline ring, benzofuran ring, indole ring, morpholine ring, pyrrolidine ring, piperidine ring, tetrahydrofuran ring and the like. Therefore, the heterocyclic group means a monovalent group derived by removing a hydrogen atom from these heterocycles. Therefore, specific examples of the heterocyclic group which may have a substituent include 2-pyridyl. Group, 3-pyridyl group, 4-pyridyl group, 2-pyrrolyl group, 3-pyrrolyl group, 2-furyl group, 3-furyl group, 2-thienyl group, 3-thienyl group, 2-imidazolyl group, 2-oxazolyl group Group, 2-thiazolyl group, piperidino group, 4-piperidyl group, morpholino group, 2-morpholinyl group, N-indolyl group, 2-indolyl group, 2-benzofuryl group, 2-benzothienyl group, 2-quinolino group, N -Carbazolyl group etc. are mentioned.

^As the halogen atom in R 1 to R ^6, fluorine, chlorine, bromine, and iodine.

In addition, the alkyl group having 1 to 4 carbon atoms in R ^{1 to} R ¹² may be linear or branched, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl group. , Sec-butyl group, and tert-butyl group.

In the naphthol azo pigment of the present invention, A is preferably a phenyl group which may have a substituent from the viewpoint of lightness. Furthermore, from the viewpoint of lightness and dispersibility, R ¹ is preferably an alkyl group having 1 to 4 carbon atoms or —OR ⁷ , and more preferably R ¹ is a methyl group or a methoxy group.

  The naphtholazo pigment of the present invention may have a chemical structure of the general formula (1), or a tautomer thereof, may be a pigment having any crystal form, and may be any so-called polymorph. It may be a mixed crystal of pigments having a crystal 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 naphthol azo pigment of the present invention are listed below, but are not limited thereto.

  The naphtholazo pigment (a1) is a water-insoluble pigment having excellent fastness to solvents and light, and by using this pigment, coloring for a color filter excellent in both luminance and contrast ratio is achieved. A composition can be obtained.

  As the colorant (a) in the coloring composition for a color filter of the present invention, the naphthol azo pigment (a1) can be used alone or in admixture of two or more.

Further, since color adjustment becomes easy, other red pigments, yellow pigments, and the like may be used in combination.
Examples of the red pigment that can be used in combination when the coloring composition for a color filter of the present invention is used for a red filter segment include 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, 166, 168, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 221, 242, 246, 254, 255, 264, 270, 272, 273, 274, 276, 277, Red pigments such as 278, 279, 280, 281, 282, 283, 284, 285, 286, and 287 can be used in combination. Among these, from the viewpoint of obtaining a high contrast ratio and high brightness, C.I. I. Pigment Red 254, 177, 176 or 242 is preferably used, and these may be used together.
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. Xanthene acid dyes such as Acid Red 52, 87, 92, 289, 338, or salt-forming compounds thereof; I. Basic Red 1, 8, C.I. I. Basic violet 10, 11 and other xanthene-based basic dyes or salts thereof.

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, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221 and the like.
Among these, C.I. can be expanded in that the chromaticity region can be expanded. I. Pigment Yellow 138, 139, 150, or 185 is preferred, and C.I. I. Pigment Yellow 139 or 150 is more preferable.
Examples of orange pigments that can be used in combination include C.I. I. Pigment orange 38, 43, 71, 73, etc. are mentioned. Among these, C.I. can be expanded in that the chromaticity region can be expanded. I. Pigment Orange 38 is preferred.
Examples of the orange dye and / or yellow dye include quinoline-based, azo-based (pyridone-based, barbituric acid-based, metal complex-based, etc.), disazo-based, and methine-based dyes.

  When used in combination with the above red pigment / dye or yellow pigment / dye, the content of the naphthol azo pigment (a1) is 10 to 100% by weight, preferably 20 to 90% by weight in the total 100% by weight of the colorant (a). %, More preferably 30 to 60% by weight. By being in this content range, the chromaticity region can be expanded.

  The naphthol azo pigment (a1) of the coloring composition of the present invention is C.I. I. Pigment Red 254, bluer, C.I. I. It is yellowish than CI Pigment Red 177, and the rising wavelength of the transmission spectrum is in the range of 570 to 590 nm. Therefore, it effectively acts on the bright line of the backlight generally used in liquid crystal display devices, and high brightness is obtained. . Further, by using the naphtholazo pigment and the resin-type dispersant (c) in combination, the pigment can stably exist in a primary particle state, and a high contrast ratio can be obtained at the same time.

[Miniaturization of pigment]
The pigment used in the present invention can be used after being refined. The naphtholazo pigment (a1) is also preferably used after being refined, but the refinement method is not particularly limited. For example, any of wet grinding, dry grinding, and dissolution precipitation can be used. As illustrated, a salt milling process by a kneader method, which is a kind of wet grinding, can be performed. As the naphthol azo pigment (a1) to be refined, any commercially available product may be used, or a naphthol azo pigment (a1) produced by a coupling reaction between a diazo compound corresponding to the naphthol azo pigment (a1) and a coupler compound may be used. Good. Moreover, it is preferable to refine and use also about the pigment used together with a naphthol azo pigment (a1), or the pigment composition containing a naphthol azo pigment (a1).

The primary particle size of the refined pigment is preferably 20 nm or more because of good dispersion in the colorant carrier. Moreover, since it can form a filter segment with high contrast ratio, it is preferable that it is 100 nm or less. A particularly preferable range is a range of 25 to 85 nm.
The primary particle diameter of the pigment was measured by directly measuring the size of the primary particle from an electron micrograph of the pigment using a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume of each particle is approximated to a cube having the obtained particle diameter to obtain an average volume, and the length of one side of the cube having this average volume is determined as the average primary The particle size.

  Salt milling is a process of heating a mixture of pigment, water-soluble inorganic salt and water-soluble organic solvent using a kneader such as a kneader, trimix, two-roll mill, three-roll mill, ball mill, attritor or sand mill. Then, after mechanically kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt serves as a crushing aid, and the pigment is crushed using the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a sharp particle size distribution with a very fine primary particle diameter and a wide distribution range.

  As the water-soluble inorganic salt, 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 weight, and most preferably 300 to 1000 parts by weight, based on 100 parts by weight of the pigment, from both the processing efficiency and the 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, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable from the viewpoint of safety because the temperature rises during salt milling and the solvent is easily evaporated. 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 and the like are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by weight, and most preferably 50 to 500 parts by weight, based on 100 parts by weight of the pigment.

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

<Resin (b)>
The resin (b) contained in the coloring composition for a color filter of the present invention disperses the colorant (a), and examples thereof include a thermoplastic resin and a thermosetting resin. The resin (b) is preferably a transparent resin having a spectral transmittance of 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 photosensitive coloring composition, it is preferable to use the alkali-soluble vinyl resin which copolymerized the acidic substituent containing ethylenically unsaturated monomer. In order to further improve the photosensitivity, an active energy ray-curable resin having an ethylenically unsaturated double bond can also be used.

  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, and polyimide resins.

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

  Examples of the vinyl-based alkali-soluble resin copolymerized with an acidic substituent-containing ethylenically unsaturated monomer include resins having an acidic substituent such as a carboxyl group and a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic substituent, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, Or an isobutylene / (anhydrous) maleic acid copolymer etc. are mentioned. Among them, at least one resin selected from an acrylic resin having an acidic substituent and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic substituent, is preferably used because of its high heat resistance and transparency. It is done.

  Examples of the active energy ray-curable resin having an ethylenically unsaturated double bond include resins into which an ethylenically unsaturated double bond has been introduced by the following methods (i) and (ii).

[Method (i)]
As the method (i), for example, a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group and one or more other monomers is used. Addition reaction of a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond, and further reacting a polybasic acid anhydride with the generated hydroxyl group to convert an ethylenically unsaturated double bond and a carboxyl group. There is a way to introduce.

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

  Examples of unsaturated monobasic acids include (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted products, etc. Monocarboxylic acid etc. are mentioned, These may be used independently or may use 2 or more types together.

  Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., and these may be used alone or in combination of two or more. It doesn't matter. If necessary, use a tricarboxylic anhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic dianhydride to increase the number of carboxyl groups. The group can be hydrolyzed. Further, when tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the ethylenically unsaturated double bonds can be further increased.

  As a method similar to the method (i), for example, a side chain of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group and one or more other monomers. There is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of a carboxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[Method (ii)]
As the method (ii), an ethylenically unsaturated monomer having a hydroxyl group is used, and an unsaturated monobasic acid monomer having another carboxyl group or another monomer is copolymerized. There is a method of reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the side chain hydroxyl group of the obtained copolymer.

Examples of the ethylenically unsaturated monomer having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3
-Or 4-hydroxybutyl (meth) acrylate, glycerol (meth) acrylate, or hydroxyalkyl methacrylates such as cyclohexanedimethanol mono (meth) acrylate, which are used alone or in combination of two or more. It may be used in combination. Further, polyether mono (meth) acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the hydroxyalkyl (meth) acrylate, polyγ-valerolactone, polyε-caprolactone, and / or Polyester mono (meth) acrylate added with poly-12-hydroxystearic acid or the like can also be used. From the viewpoint of suppressing foreign matter on the coating film, 2-hydroxyethyl methacrylate or glycerol methacrylate is preferable.

  Examples of the ethylenically unsaturated monomer having an isocyanate group include 2- (meth) acryloyloxyethyl isocyanate or 1,1-bis [methacryloyloxy] ethyl isocyanate, but are not limited thereto. Two or more types can be used in combination.

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

  In addition, from the viewpoint of dispersibility, stability, developability, and heat resistance of the colorant (a), as a colorant adsorption group and a carboxyl group that acts as an alkali-soluble group during development, an affinity group for the colorant carrier and the solvent The balance between the working aliphatic group and the aromatic group is important for the dispersibility of the pigment, the developer permeability in the coating film, the developer solubility of the uncured part, and the durability. The acid value is 20 to 300 mgKOH / g. It is preferable to use this resin. 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. If it exceeds 300 mgKOH / g, a fine pattern may not remain.

  The resin (b) is preferably used in an amount of 30 parts by weight or more with respect to 100 parts by weight of the total weight of the colorant (a) because the film formability and various resistances are good, and the colorant concentration is high. From the viewpoint that good color characteristics can be expressed, it is preferably used in an amount of 500 parts by weight or less. More preferably, it is 100-400 weight part. More preferably, it is 160-320 weight part. The chromaticity region can be expanded by such a composition ratio of the pigment.

<Resin type dispersant (c)>
The resin type dispersant (c) in the present invention is a resin type dispersant having a basic substituent. The resin-type dispersant (c) of the present invention has a pigment-affinity unit containing a basic substituent that adsorbs to the naphthol azo pigment (a1) and a unit compatible with the pigment carrier, and includes a naphthol azo pigment. It functions to stabilize the dispersion of (a1) on the pigment carrier.

  Among the resin-type dispersants (c), the resin-type dispersant having a basic substituent containing a nitrogen atom is more excellent in the dispersion stability of the coloring composition and is preferable.

  As a number average molecular weight of the resin type dispersing agent (c) used by this invention, 500-50000 are preferable normally, and 3000-30000 are especially more preferable. When the number average molecular weight is less than 500, the effect of steric repulsion due to the pigment affinity group, the effect of compatibility with the pigment carrier, and the effect of compatibility with the pigment carrier and solvent when using a solvent are small, It may be difficult to prevent aggregation of the pigment, and the viscosity of the dispersion may increase. On the other hand, if the number average molecular weight is 50000 or more, the amount of resin added for dispersion increases, and the pigment concentration in the coating film may be lowered.

  The amine value of the resin-type dispersant (c) is preferably 35 to 100 mgKOH / g. More preferably, it is 50-75 mgKOH / g. If the amine value is less than 35 mg KOH / g, the pigment may not be sufficiently adsorbed and may result in poor dispersion. If the amine value exceeds 100 mg KOH / g, the naphthol azo pigment (a1) may be adsorbed or reacted with acidic components in the pigment carrier. In some cases, the adsorption efficiency with respect to the liquid becomes poor, resulting in poor dispersion.

  As the resin type dispersant (c), various types of resin systems such as vinyl, urethane, polyester, polyether, or polyamide can be used, but the resin design is easy and the vinyl system has excellent resistance. Monomer copolymer type is preferable, and specifically, a copolymer resin of an N, N-disubstituted amino group-containing vinyl monomer unit, an alkyl (meth) acrylate monomer unit, and other vinyl monomer units is preferable. It is.

  As N, N-disubstituted amino group-containing vinyl monomer units, N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, Examples thereof include N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, and N, N-diethylaminoethyl (meth) acrylamide, but are not necessarily limited thereto. These monomer units are adsorbed to the naphthol azo pigment (a1) as basic group-containing monomer units.

  As alkyl (meth) acrylate monomer units, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, It is obtained by the reaction of unsaturated monocarboxylic acid such as 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, or lauryl (meth) acrylate with alkyl alcohol having 1 to 18 carbon atoms (meta ) Acrylic esters and the like, but are not necessarily limited thereto. These monomer units act as pigment carrier affinity groups.

  Other vinyl monomer units include nitro group-containing vinyl monomers such as (meth) acrylonitrile, vinyl aromatic monomers such as styrene, α-methylstyrene, or benzyl (meth) acrylate, 2-hydroxyethyl ( Hydroxyl group-containing vinyl monomers such as (meth) acrylate, hydroxypropyl (meth) acrylate, or polyethylene glycol (meth) acrylate, (meth) acrylamide, N, N-dimethylacrylamide, N-isopropylacrylamide, diacetone acrylamide, etc. Amide group-containing vinyl monomers, vinyl monomers such as N-methylol (meth) acrylamide or dimethylol (meth) acrylamide, N-methoxymethyl (meth) acrylamide, or N-butoxime Alkoxymethyl group-containing vinyl monomers such as ru (meth) acrylamide, olefins such as ethylene, propylene or isoprene, dienes such as chloroprene or butadiene, methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, Examples thereof include vinyl ethers such as n-butyl vinyl ether or isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate or vinyl propionate, which are appropriately used according to the purpose, but are not necessarily limited thereto.

  Polymers having primary amino group-containing monomer units such as allylamine, or polyethyleneimine, polyethylene polyamine, polyxylylene poly (hydroxypropylene) polyamine, or poly (aminomethylated) epoxy resin, polyester resin, acrylic resin Alternatively, a resin-type dispersant having a comb-shaped basic substituent modified with a polyether resin or the like can also be mentioned.

  As a commercial item of such a resin type dispersing agent (c), for example, DISPERBYK 161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001 manufactured by BYK Japan 2050, 2150, 2163, 2164, BYK-LPN6919, SOLPERSE11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, manufactured by Nippon Lubrizol Corporation 38500, 39000, 53095, 56000, 71000, EFKA4300, 4330, 4046, 4060, 4080 manufactured by BASF, Ajinomoto Fine Techno Co., Ltd. Of AJISPER PA111, PB711, PB821, PB822, PB824, and the like.

As the resin-type dispersant (c) of the red coloring composition for a color filter of the present invention, particularly preferred is a basic copolymer block (A) and a pigment carrier affinity copolymer block (B). It is a block copolymer resin and the basic copolymer block (A) preferably contains a nitrogen atom.
Hereinafter, the resin type dispersant which is a block copolymer will be described.

(Block copolymer)
The resin-type dispersant (c) is a site having a high affinity for the pigment carrier, which has the effect of adsorbing the pigment (hereinafter abbreviated as an adsorbing part) and preventing the aggregation of the pigments and improving the dispersibility. Hereinafter, it is abbreviated as an affinity part. The basic copolymer block (A), which is an adsorption part for the naphtholazo pigment (a1), and the pigment carrier affinity copolymer block (B), which is an affinity part for the pigment carrier, are separated on the same molecule. By using the block copolymer used as a resin-type dispersant, a red colored composition in which the naphtholazo pigment (a1) is finely and low-viscosity and stably dispersed without impairing its color characteristics is provided. can do.

  Various resin systems can be selected for the basic copolymer block (A) and the pigment carrier affinity copolymer block (B) constituting the block copolymer, but the resin design is easy and A vinyl copolymer having excellent resistance is desirable. Hereinafter, each copolymer block will be described.

"Basic copolymer block (A)"
Specific examples of the basic copolymer block (A) include N, N-dimethylaminoethyl (meth) acrylate, N, N-diethylaminoethyl (meth) acrylate, N, N-dimethylaminopropyl (meth) acrylate, N N, N-diethylaminopropyl (meth) acrylate, N, N-dimethylaminoethyl (meth) acrylamide, N, N-diethylaminoethyl (meth) acrylamide and the like having N, N-disubstituted amino group-containing vinyl monomer units Polymers, polymers having primary amino group-containing monomer units such as allylamine, polyethyleneimine, polyethylene polyamine, polyxylylene poly (hydroxypropylene) polyamine, poly (aminomethylated) epoxy resin, etc. Yes, but not necessarily limited to these Not.

  Among these, a copolymer having an N, N-disubstituted amino group-containing vinyl monomer unit, which is easy to design a resin of the block copolymer and excellent in various resistances, is preferable. The N, N-disubstituted amino group-containing vinyl monomer unit contained in the combined block (A) is 60 to 100% by weight, more preferably 80 to 100% by weight, and the N, N-disubstituted amino group is contained. The vinyl monomer unit other than the vinyl monomer unit is preferably a vinyl monomer unit described in the pigment carrier affinity copolymer block (B).

More preferably, it has a structural unit represented by the following structural formula from the viewpoint of the stability of the coloring composition.

[In General Formula (2), R ³⁴ is a hydrogen atom or a methyl group, R ³⁵ is an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH—R ^g — group, a —COO—R ^h — group (provided that R ^g and R ^h are a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R′—O—R ″ —: R ′ and R ″ are each independently an alkylene group) ). n3 is an integer of 0 or 1, and R ^{36 to} R ³⁸ represent a cyclic or chain alkyl group which may have a substituent, an aryl group which may have a substituent, or a substituent. Represents an aralkyl group which may be present, and X ¹⁻ represents a counter anion in the case of n3 = 1. ]

As X ¹⁻ of the counter anion, Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ −, BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ^{− and the} like can be mentioned.

Among them, R ^{36 to} R ³⁸ are preferably a methyl group, an ethyl group, a benzyl group or the like, X ¹⁻ is preferably Cl ⁻ or the like, and R ³⁵ is preferably a methylene group, an ethylene group or the like.
Moreover, it is preferable to have a quaternary ammonium base in which n3 = 1, and it is also preferable to have a tertiary amino group in which n = 0.

  Two or more repeating units containing an amino group as described above may be contained in one B block. In that case, the repeating unit containing 2 or more types of amino groups may be contained in the B block in any form of random copolymerization or block copolymerization.

In —N ⁺ R ³⁶ R ³⁷ R ³⁸ of the general formula (2), two or more of R ³⁶ , R ³⁷ and R ³⁸ may be bonded to each other to form a cyclic structure, for example, 5 to 7 Examples thereof include a membered nitrogen-containing heterocyclic monocycle or a condensed ring formed by condensing two of them. The nitrogen-containing heterocycle preferably has no aromaticity, more preferably a saturated ring. Specifically, the thing of a following formula (C) is mentioned, for example.

These cyclic structures may further have a substituent. As ^R 36 ^{to R 38} in ^{-N + R 36 R 37 R 38} , more preferred are an alkyl group having 1 to 3 carbon atoms which may have a substituent, which may have a substituent aralkyl Or a phenyl group which may have a substituent.

In the general formula (2), examples of the divalent linking group R ³⁵ include, for example, an alkylene group having 1 to 10 carbon atoms, an arylene group, a —CONH—R ^g — group, a —COO—R ^h — group (provided that R ^g and R ^h are a direct bond, an alkylene group having 1 to 10 carbon atoms, or an ether group having 1 to 10 carbon atoms (—R′—O—R ″ —: R ′ and R ″ are each independently an alkylene group) And is preferably a —COO—R ^h — group. Among the —COO—R ^h — groups, R ^h is more preferably a methylene group, an ethylene group, a propylene group, or a butylene group, and particularly preferably an ethylene group.

As the structural unit represented by the general formula (2), (meth) acryloylaminopropyltrimethylammonium chloride, (meth) acryloyloxyethyltrimethylammonium chloride, (meth) acryloyloxyethyl (4-benzoylbenzyl) dimethylammonium bromide (Meth) acryloyloxyethylbenzyldimethylammonium chloride is preferred, and (meth) acryloyloxyethylbenzyldimethylammonium chloride is particularly preferred from the viewpoint of pigment dispersibility.
Two or more of these structural units may be contained.

Moreover, it can be confirmed, for example, by the following method that the pigment dispersant according to the present invention contains a quaternary ammonium halogen salt which is one of the above general formulas (2). The presence of ionic halogen can be detected by vigorously stirring the sample alone or the organic solvent solution of the sample with pure water, adding an aqueous silver nitrate solution to the aqueous layer, and generating insoluble matter. Also, quaternary ammonium to be paired can be detected by showing absorption in 2900～3300Cm ^-1 and 1300～1500Cm ^-1 in the infrared absorption spectrum analysis.

"Pigment carrier affinity copolymer block (B)"
The monomer that is a precursor of the pigment carrier affinity copolymer block (B) does not have a functional group containing a nitrogen atom such as an amino group and can be copolymerized with a monomer constituting the A-block. There is no particular limitation.
For example, styrene monomers such as styrene and α-methylstyrene; methyl (meth) acrylate, ethyl (meth) acrylate (propyl) (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth ) Octyl acrylate, 2-ethylhexyl (meth) acrylate, glycidyl (meth) acrylate, benzyl (meth) acrylate, hydroxyethyl (meth) acrylate, glycidyl ethyl acrylate, polyethylene glycol (meth) acrylate, polypropylene glycol (meth) (Meth) acrylic acid ester monomers such as acrylates; (meth) acrylic acid salt monomers such as (meth) acrylic acid chlorides; vinyl acetate monomers; allyl glycidyl ether, crotonic acid glycidyl ether Any polymer structure obtained by copolymerizing comonomers including glycidyl ether monomers.

  In particular, the B-block contains a polyalkylene glycol (meth) acrylate such as polyethylene glycol (meth) acrylate and polypropylene glycol (meth) acrylate as a copolymerization component (that is, a partial structure derived from polyalkylene glycol (meth) acrylate). In particular, and preferably has a partial structure represented by the following general formula (I).

[In General Formula (I), n represents an integer of 1 to 5, and R ³⁹ represents a hydrogen atom or a methyl group. ]

  As for the partial structure represented by general formula (I), it is especially preferable that 5-40 mol% is contained in B-block.

  Further, from the viewpoint of enhancing the dispersion stability, the B-block further contains 50 to 90 mol of a structural unit having a (meth) acrylic acid ester monomer other than the partial structure represented by the general formula (I) as a precursor. It is preferable to contain%, More preferably, it is 60-80 mol%. Among them, (meth) acrylic acid ester monomers include (meth) methyl acrylate, (meth) ethyl acrylate (propyl meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, (meth) It is preferable to use octyl acrylate because the dispersibility and stability of the coloring composition are excellent.

  By including the partial structure represented by the general formula (I) in the B-block, hydrophilicity is imparted and the solubility in the developer is improved. On the other hand, the compatibility with the binder resin is increased and the dispersion stability is improved by further including a structural unit having a (meth) acrylate monomer other than the partial structure represented by the general formula (I) as a precursor. .

  The pigment carrier affinity copolymer block (B) preferably contains 0% by weight of vinyl monomer units containing amino groups, but may be contained if it is less than 10% by weight.

"Production method of block copolymer"
The block copolymer can be produced by a known method. In particular, (1) a method using living polymerization, or (2) a precursor of a basic copolymer block (A) having a functional group at the terminal. A polymer coupling method in which (a) and a precursor (b) of a pigment carrier affinity copolymer block (B) having a functional group at the terminal are reacted is preferable. Among these, (1) a method using living polymerization is particularly preferable.

(1) Living polymerization method In the living polymerization method, side reactions occurring in general radical polymerization are suppressed, and further, the growth of polymerization occurs uniformly, so that a block polymer or a resin having a uniform molecular weight can be easily synthesized.
Above all, the atom transfer radical polymerization method using organic halides and sulfonyl halide compounds as initiators and transition metal complexes as catalysts can be applied to a wide range of monomers and employs a polymerization temperature applicable to existing equipment. It is preferable in that it can be performed. An atom transfer radical polymerization method can be performed by the method described in the following references 1 to 8 and the like.
(Reference 1) Fukuda et al., Prog. Polym. Sci. 2004, 29, 329
(Reference 2) Matyjaszewski et al., Chem. R ev. 2001, 101, 2921
(Reference 3) Matyjaszewski et al. Am. Chem. Soc. 1995, 117, 5614
(Reference 4) Macromolecules 1995, 28, 7901, Science, 1996, 272, 866
(Reference 5) Pamphlet of International Publication No. 96/30421 (Reference 6) Pamphlet of International Publication No. 97/18247 (Reference 7) JP-A-9-208616 (Reference 8) JP-A-8-411117

  In the atom transfer radical polymerization method, a transition metal complex such as copper, ruthenium, iron and nickel is used as a redox catalyst. Specific examples of the transition metal complex include low-valent halogenated transition metals such as copper (I) chloride and copper (I) bromide. In order to control the polymerization rate, a well-known method is used. High valent transition metals such as copper (II) chloride and copper (II) bromide may be added to the polymerization system.

  An organic ligand is used for the metal complex. Organic ligands are used to allow reversible changes in solubility in the polymerization solvent and redox conjugated complexes. Examples of the metal coordination atom include a nitrogen atom, an oxygen atom, a phosphorus atom, and a sulfur atom, and a nitrogen atom or a phosphorus atom is preferable. Specific examples of the organic ligand include sparteine, 2,2′-bipyridyl and derivatives thereof, 1,10-phenanthroline and derivatives thereof, tetramethylethylenediamine, pentamethyldiethylenetriamine, tris (dimethylaminoethyl) amine, hexamethyl ( 2-aminoethyl) amine, triphenylphosphine, and tributylphosphine. Among the above catalysts, polymerization is preferably performed using a combination of copper halide and tetraethylenediamine in view of controlling the polymerization rate and the molecular weight of the block resin.

The transition metal and the organic ligand may be added separately to form a metal complex in the polymer, or the metal complex may be synthesized in advance and added to the polymerization system. In particular, when the transition metal is copper, the former method is preferable, and for the ruthenium, iron, and nickel, the latter method is preferable.
Specific examples of ruthenium, iron and nickel complexes synthesized in advance include tristriphenylphosphinoniruthenium chloride (Ru (Cl) ₂ (PPh ₃ ) ₃ , bistrisphenylphosphinoniiron chloride (Fe (Cl) ₂ (PPh ₃ ) ₂ ), nickel bistrisphenylphosphinonichloride (Ni (Cl) ₂ (PPh ₃ ) ₂ ), nickel bistributylphosphinonibromide (NiBr ₂ (PBu ₃ ) ₂ ) and the like. .

  As the initiator used in the atom transfer radical polymerization method, known initiators can be used, and organic halides having a highly reactive carbon halogen bond, sulfonyl halide compounds and the like are mainly used. Specific examples include ethyl bromoisobutyrate, ethyl bromobutyrate, ethyl chloroisobutyrate, ethyl chlorobutyrate, p-toluenesulfonic acid chloride, bromoethylbenzene, and chloroethylbenzene. These are used alone or in combination.

  In the above atom transfer radical polymerization, the initiator of the atom transfer radical polymerization is appropriately selected according to the molecular weight of the resin to be synthesized, but is preferably 0.001 to 10 mol% based on the total amount of the radical polymerizable monomer. Preferably it is used in a proportion of 0.01 to 1 mol%.

  The amount of transition metal used is preferably 0.03 to 3 moles, more preferably 0.1 to 2 moles per mole of initiator as a form of halide or the like. Further, the ligand is used in a proportion of usually 1 to 5 mol, preferably 1.2 to 3 mol, per 1 mol of the transition metal (form of halide, etc.). When the above-mentioned atom transfer radical polymerization initiator, transition metal and ligand are used in such proportions, it is preferable in terms of the reactivity of living radical polymerization, the molecular weight of the produced polymer, and the like.

  In addition, due to the characteristics of atom transfer radical polymerization, the resulting resin has an active carbon-halogen bond at the terminating end, which can be modified by a known method to introduce a functional group. Moreover, it can superpose | polymerize with the polymerization initiator which has a functional group, can introduce | transduce a functional group to the resin terminal, and can utilize for various reactions.

  Atom transfer radical polymerization can be carried out without a solvent, or may be carried out in the presence of a solvent such as butyl acetate, toluene, xylene, anisole, methyl ethyl ketone, or cyclohexanone. In particular, a ketone solvent is preferable from the viewpoint of polymerization rate, and methyl ethyl ketone is particularly preferable. In the case of using a solvent, in order to prevent a decrease in polymerization rate, the amount of the solvent used after the polymerization is preferably 50% by weight or less. Even when there is no solvent or a small amount of solvent, there is no particular safety problem with respect to control of polymerization heat and the like. Rather, reduction of the solvent is preferable in terms of economy and environmental measures.

  The polymerization conditions are 60 to 130 ° C. polymerization temperature from the point of polymerization rate and catalyst deactivation, and depending on the final molecular weight and polymerization temperature, the polymerization time may be about 1 to 100 hours. . The polymerization reaction is preferably performed in an inert gas atmosphere such as nitrogen or argon in order to prevent deactivation of the polymerization catalyst by oxygen.

  After completion of the polymerization reaction, the polymerization reaction system is preferably cooled to 0 ° C. or less, more preferably about −78 ° C. to stop the reaction, and the remaining monomer and / or solvent is removed according to a well-known method. Reprecipitation in the medium and filtration of the precipitated polymer can be performed by centrifugation, washing of the polymer and drying. The block resin used in the present invention can be obtained by removing the transition metal and the like contained in the polymerization system by a known method, if necessary, and then evaporating the volatile components. As the removal method, the reaction mixture is diluted with an organic solvent such as tetrahydrofuran, toluene, or methyl ethyl ketone, washed with water / dilute hydrochloric acid or an aqueous amine solution, and the resin solution is contacted with a cation exchange resin or a chelate resin. There are a method of passing through a silica or clay column or pad, a method of filtering and centrifuging after adding an adsorbent such as a reducing agent or hydrotalcite. From the viewpoint of ease of processing, it is preferable to add a cation exchange resin and an acid adsorbent such as hydrotalcite to the diluted resin solution and stir, and filter the ion exchange resin and the acid adsorbent to obtain a resin solution. .

  When water is mixed into the resin solution by the purification treatment, the reaction between the block resin used in the present invention and the curing agent may be hindered. For example, a solvent miscible with water may be added to the resin solution and subjected to azeotropic dehydration, etc. It is desirable to remove moisture from the resin solution by treatment.

  In the atom transfer radical polymerization used in the present invention, in order to suppress side reactions that occur during general radical polymerization, depending on the charging ratio of the initiator of the atom transfer radical polymerization added during polymerization and the radical polymerizable monomer, The molecular weight of the resin and the ratio of the basic copolymer block (A) or the pigment carrier affinity copolymer block (B) can be freely controlled.

(2) Polymer coupling method Functional group at the terminal of the precursor (a) of the basic copolymer block (A) and the precursor (b) of the pigment carrier affinity copolymer block (B) in the polymer coupling method Specific examples of preferable examples include a carboxyl group, a primary amino group, a hydroxyl group, and an alkoxysilyl group.

  As a method for introducing a terminal functional group into the precursor (a) of the basic copolymer block (A) and the precursor (b) of the pigment carrier affinity copolymer block (B), the functional groups listed above are used. A method of radical polymerization using a chain transfer agent having a thiol group is preferred. The chain transfer agent having a carboxyl group is mercaptopropionic acid, the chain transfer agent having a primary amino group is cysteamine, the chain transfer agent having a hydroxyl group is mercaptoethanol, and the chain transfer agent having an alkoxysilyl group is 3- Examples include mercaptopropylmethylmethoxysilane and 3-mercaptopropyltrimethoxysilane.

  The reaction between the precursor (a) and the precursor (b) can be carried out by a known reaction with a combination of the following Table 1, for example.

  Examples of the binder polyisocyanate compound include aromatic polyisocyanate, aliphatic polyisocyanate, araliphatic polyisocyanate, and alicyclic polyisocyanate. Examples of the aromatic polyisocyanate include 1,3-phenylene diisocyanate, 4,4′-diphenyl diisocyanate, 1,4-phenylene diisocyanate, 4,4′-diphenylmethane diisocyanate, 2,4-tolylene diisocyanate, 2,6 -Tolylene diisocyanate, 4,4'-toluidine diisocyanate, 2,4,6-triisocyanate toluene, 1,3,5-triisocyanate benzene, dianisidine diisocyanate, 4,4'-diphenyl ether diisocyanate, or 4,4 ' , 4 "-triphenylmethane triisocyanate, etc. Examples of the aliphatic polyisocyanate include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, Examples thereof include tamethylene diisocyanate, 1,2-propylene diisocyanate, 2,3-butylene diisocyanate, 1,3-butylene diisocyanate, dodecamethylene diisocyanate, or 2,4,4-trimethylhexamethylene diisocyanate. Examples of the polyisocyanate include ω, ω′-diisocyanate-1,3-dimethylbenzene, ω, ω′-diisocyanate-1,4-dimethylbenzene, ω, ω′-diisocyanate-1,4-diethylbenzene, 1, Examples include 4-tetramethylxylylene diisocyanate or 1,3-tetramethylxylylene diisocyanate, etc. Examples of the alicyclic polyisocyanate include 3-isocyanate methyl-3,5,5-trimethylcyclohexane. Xyl isocyanate, 1,3-cyclopentane diisocyanate, 1,3-cyclohexane diisocyanate, 1,4-cyclohexane diisocyanate, methyl-2,4-cyclohexane diisocyanate, methyl-2,6-cyclohexane diisocyanate, 4,4′-methylenebis ( Cyclohexyl isocyanate), 1,4-bis (isocyanate methyl) cyclohexane, 1,4-bis (isocyanate methyl) cyclohexane, etc., but are not necessarily limited to these, and some of the above poly A trimethylolpropane adduct of isocyanate, a burette reacted with water, a trimer having an isocyanurate ring, and the like can also be used in combination.

  As the polyepoxy compound of the binder, a polyepoxy compound having at least two glycidyl groups is preferable. Specifically, ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, trimethylolpropane triglycidyl ether, trimethylolethane triglycidyl ether, sorbitol polyglycidyl ether, or penta Aliphatic polyepoxy compounds such as erythritol polyglycidyl ether, aromatic polyepoxy compounds of the bisphenol A or bisphenol F type, tetraglycidylaminophenylmethane, triglycidyl isocyanurate, or 1,3-bis (N, N-glycidylaminomethyl) ) Glycidylamine type epoxy compounds such as cyclohexane, but are not necessarily limited to these Not intended to be.

  The constituent weight ratio of the basic copolymer block (A) and the pigment carrier affinity copolymer block (B) and the number average molecular weight of each block are the number average molecular weight and amine value of the resin type dispersant as a whole. It is preferable that it can be designed arbitrarily so as to be in the preferable range.

  In the red coloring composition of the present invention, the content of the resin-type dispersant (c) having a basic substituent is preferably 5 to 70 parts by weight, more preferably 10 parts per 100 parts by weight of the colorant (a). ~ 50 parts by weight. If it is less than 5 parts by weight, the dispersibility may be deteriorated, and if it exceeds 70 parts by weight, the heat resistance and light resistance may be deteriorated.

  In the present invention, in addition to the above resin type dispersant (c), other resin type dispersants may be included, and a resin type dispersant having an acidic group may be used in combination.

<Solvent (d)>
The solvent (d) is a filter segment in which a colorant is sufficiently dispersed in a resin, and the colored composition of the present invention is applied on a transparent substrate such as a glass substrate so that the dry film thickness is 0.2 to 5 μm. Is used to facilitate the formation.
As the solvent (d), 1,2,3-trichloropropane, 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-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate N-methylpyrrolidone, 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, ethyl Lenglycol 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 Nopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate , Propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, vinegar n- butyl, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.
These solvents can be used singly or in combination of two or more at any ratio as required.

  Among them, glycol acetates such as propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and the like because of good dispersibility of the naphtholazo pigment (a1) of the present invention. , Alcohols such as propyl alcohol and butyl alcohol, aromatic alcohols such as benzyl alcohol, ethyl ether, isopropyl ether, dioxane, tetrahydrofuran, furfural, 1.3 dioxolane, dibutyl ether, ethers such as methyl tert-butyl ether, ethylene Glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether It is preferable to use ketones such as glycol ethers and cyclohexanone and diethylene glycol monomethyl ether.

  Since the solvent (d) can adjust the colored composition to an appropriate viscosity to form a filter segment having a desired uniform film thickness, the amount of the solvent (d) is 800 to 4000 parts by weight with respect to 100 parts by weight of the colorant (a). It is preferable to use in.

<Dye derivative (e)>
The coloring composition for a color filter of the present invention can preferably use a pigment derivative (e). The dye derivative (e) is excellent in dispersion of the naphthol azo pigment (a1) and has a large effect of preventing reaggregation of the naphthol azo pigment (a1) after dispersion.
As the pigment derivative (e), a basic substituent, an acidic substituent, or an optionally substituted phthalimidomethyl group is introduced into an organic pigment, β-naphthol compound, acridone compound or triazine compound. And the like.

  In particular, the organic pigment preferably contains a pigment derivative having an acidic substituent or a metal salt thereof. Dye derivatives that have acidic substituents or their metal salts in organic pigments promote the pigment adsorption of pigments and resin-type dispersants, and improve the dispersibility of pigments, thus preventing re-aggregation of pigments after dispersion Is big. Therefore, when using a coloring composition in which a pigment is dispersed in a pigment carrier using a dye derivative having an acidic substituent or a metal salt thereof, a color filter having excellent stability can be obtained. Furthermore, it is preferable to use the resin-type dispersant having a basic substituent containing a nitrogen atom at the same time because dispersibility is further improved. This is considered to promote the pigment adsorption of the dispersant by the acid-base interaction between the acidic substituent of the dye derivative arranged in the vicinity of the pigment and the basic substituent of the dispersant.

That is, the structure of the pigment derivative (e) that can be used in the present invention is a compound represented by the following general formula (3).
P-Lx General formula (3)
(However,
P: organic pigment residue, β-naphthol residue, acridone residue or triazine residue L: basic substituent, acidic substituent, or optionally substituted phthalimidomethyl group x: hydrogen atom or metal Ion. )

  Examples of the organic pigment constituting the organic pigment residue of P include, for example, diketopyrrolopyrrole pigments; azo pigments such as azo, disazo and polyazo; phthalocyanine pigments such as copper phthalocyanine, halogenated copper phthalocyanine and metal-free phthalocyanine Anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavantron, anthanthrone, indanthrone, pyranthrone, violanthrone; quinacridone pigment; dioxazine pigment; perinone pigment; perylene pigment; thiaindigo pigment; Indoline pigments; isoindolinone pigments; quinophthalone pigments; selenium pigments; metal complex pigments.

  Β-naphthol constituting the β-naphthol residue of P is an alkyl group (methyl group, ethyl group, butyl group, etc.), amino group, alkylamino group (dimethylamino group, diethylamino group, dibutylamino group, etc.), nitro Group, hydroxyl group, alkoxy group (methoxy group, ethoxy group, butoxy group, etc.), halogen (chlorine, bromine, etc.), phenyl group (alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) And a substituent such as a phenylamino group (which may be substituted with an alkyl group, amino group, alkylamino group, nitro group, hydroxyl group, alkoxy group, halogen, etc.) It is also a good β-naphthol.

  Examples of the acidic substituent for L include sulfonic acid, carboxylic acid, and phosphoric acid.

Examples of the metal ion of x include alkali metal ions such as sodium and potassium, alkaline earth metal ions such as magnesium, calcium and barium, amphoteric metal ions such as aluminum and zinc, and transition metal ions such as iron and nickel. .
Of these, alkaline earth metal ions such as calcium and barium, amphoteric metal ions such as aluminum and zinc, and transition metal ions such as iron and nickel are preferable. Of these, aluminum ions are particularly preferred because of their high heat resistance and dispersibility.

  The matrix skeleton is preferably a dye derivative in which P in the general formula (3) is an organic pigment residue, β-naphthol residue, or triazine residue, and among them, thiaindigo pigments and diketopyrrolopyrrole pigments. Organic pigment residues, β-naphthol residues, or triazine residues that are pigments or anthraquinone pigments are preferred.

  That is, in the colored composition of the present invention, P in the general formula (2) is an organic pigment residue, β-naphthol residue, or triazine residue, and L in the general formula (2) is an acidic substituent. A pigment derivative having an acidic substituent, a β-naphthol derivative having an acidic substituent, or a triazine derivative having an acidic substituent is preferable from the viewpoint of dispersion stability. Among them, the naphthol azo derivative having an acidic substituent is excellent in the dispersion of the naphthol azo pigment (a1) and has the greatest effect of preventing reaggregation of the naphthol azo pigment after the dispersion.

  In the present invention, the blending amount of the dye derivative (e) is preferably 1 part by weight or more, more preferably 5 parts by weight or more, most preferably 100 parts by weight of the naphthol azo pigment (a1) from the viewpoint of improving dispersibility. Is 10 parts by weight or more. Further, from the viewpoint of heat resistance and light resistance, the amount is preferably 25 parts by weight or less, and most preferably 20 parts by weight or less with respect to 100 parts by weight of the naphtholazo pigment (a1).

  The coloring composition for color filters of the present invention can be used as a photosensitive coloring composition (resist material) for color filters by further adding a photopolymerizable monomer and / or a photopolymerization initiator.

<Photopolymerizable monomer>
The photopolymerizable monomer used in the present invention includes monomers or oligomers that are cured by ultraviolet rays or heat to form a resin, and these can be used alone or in combination of two or more.

  Examples of the photopolymerizable monomer include methyl methacrylate, ethyl methacrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, cyclohexyl methacrylate, β-carboxyethyl methacrylate, polyethylene glycol dimethacrylate, 1,6-hexanediol dimethacrylate, triethylene glycol dimethacrylate, tripropylene glycol dimethacrylate, trimethylolpropane trimethacrylate, pentaerythritol trimethacrylate, pentaerythritol tetramethacrylate, 1,6-hexanediol di Glycidyl ether dimethacrylate, bisphenol A diglycidyl ether dimethacrylate, neopentyl grease Diglycidyl ether dimethacrylate, dipentaerythritol hexamethacrylate, dipentaerythritol pentamethacrylate, tricyclodecanyl methacrylate, ester acrylate, methylolated melamine methacrylate, epoxy methacrylate, urethane acrylate, etc. Acrylic acid ester and methacrylic acid ester, acrylic acid, methacrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, methacrylamide, N-hydroxymethylmethacrylamide, N-vinylformamide, acrylonitrile However, it is not necessarily limited to these.

  The content of the photopolymerizable monomer is preferably 5 to 400 parts by weight with respect to 100 parts by weight of the colorant (a), and 10 to 300 parts by weight from the viewpoint of photocurability and developability. Is more preferable.

<Photopolymerization initiator>
In the colored composition for color filter of the present invention, when the composition is cured by ultraviolet irradiation and a filter segment is formed by a photolithography method, a photopolymerization initiator or the like is added to add a solvent development type or an alkali development type photosensitive. Can be prepared in the form of an ionic coloring composition.

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 ben Benzoin compounds such as rudimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4′-methyldiphenyl sulfide, or 3,3 ′, 4 Benzophenone compounds such as 4,4′-tetra (t-butylperoxycarbonyl) benzophenone; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, etc. 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -s-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl-4,6-bis (trichloromethyl) -S-triazine, 2,4-bis (trichloromethyl) -6-styryl-s-triazine, 2- (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- (4 Triazine compounds such as' -methoxystyryl) -6-triazine; 1,2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)], or O Oxime ester compounds such as (acetyl) -N- (1-phenyl-2-oxo-2- (4′-methoxy-naphthyl) ethylidene) hydroxylamine; bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide Or phosphine compounds such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds Or a titanocene compound or the like is used.
These photoinitiators can be used individually by 1 type or in mixture of 2 or more types by arbitrary ratios as needed.

  The content of the photopolymerization initiator is preferably 5 to 200 parts by weight with respect to 100 parts by weight of the colorant (a), and more preferably 10 to 150 parts by weight from the viewpoint of photocurability and developability. preferable.

<Sensitizer>
Furthermore, the 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) benzopheno And 4,4′-diethylaminobenzophenone.
These sensitizers can be used singly or in combination of two or more at any ratio as necessary.

  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.

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

<Amine compound>
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. The content of the leveling agent is usually preferably 0.003 to 0.5% by weight in 100% by weight of the total weight of the coloring composition.

  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. The content of the curing accelerator is preferably 0.01 to 15 parts by weight based on the total weight of the thermosetting resin (100 parts by weight).

<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 parts by weight relative to 100 parts by weight of the total weight of the colorant (a).

  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 parts by weight, preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the total weight of the colorant (a).

<Method for producing colored composition>
The coloring composition for a color filter of the present invention comprises a coloring agent (a) containing a naphthol azo pigment (a1), a resin-type dispersant (c), and a resin (b), a solvent (d), and a dye as necessary. The derivative (e) can be produced by finely dispersing together (pigment dispersion) using various dispersing means such as a three-roll mill, a two-roll mill, a sand mill, a kneader, a trimix, or an attritor. The colored composition for a color filter of the present invention may be prepared by dispersing naphtholazo pigment (a1) and other colorants such as red pigment and yellow pigment used together or separately dispersed. Can also be manufactured

  Moreover, when using as a photosensitive coloring composition (resist material) for color filters, it can prepare as a solvent developing type or an alkali developing type coloring composition. The solvent development type or alkali development type coloring composition comprises the pigment dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other dispersants, and additives. Can be mixed and adjusted. The photopolymerization initiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

<Removal of coarse particles>
The colored composition for a color filter of the present invention is a coarse particle having a size of 5 μm or more, preferably a coarse particle having a size of 1 μm or more, more preferably a coarse particle having a size of 0.5 μm or more. It is preferable to remove the mixed dust. Thus, it is preferable that the coloring composition for color filters substantially does not contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
The color filter of the present invention is a color filter comprising at least one filter segment formed of the coloring composition for a color filter of the present invention.
The color filter comprises at least one red filter segment, at least one green filter segment, and at least one blue filter segment, and the at least one red filter segment is a red coloring composition for a color filter of the present invention. It is preferable to use a product.

  The green filter segment can be formed using a normal green coloring composition. Examples of the green coloring composition include C.I. I. Pigment Green 7, 10, 36, 37, 58, and the like. Green coloring compositions 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 It can be used in combination with the yellow pigments such as 181,182,185,187,188,193,194,198,199,213,214. Further, a basic dye exhibiting yellow and a salt-forming compound of an acid dye can be used in combination.

  Moreover, a blue filter segment can be formed using a normal blue coloring composition. Examples of the blue coloring composition include C.I. I. Pigment Blue 15, 15: 1, 15: 2, 15: 3, 15: 4, 15: 6, 16, 22, 60, 64, and the like. Blue coloring compositions include C.I. I. Pigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, and other purple pigments can be used in combination. 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 lightness.

<Color filter manufacturing method>
The color filter of the present invention can be produced by a printing method or a photolithography method.
[Printing 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.

[Photolithography]
When forming a filter segment by a photolithography method, the photosensitive coloring composition prepared as the solvent development type or alkali development type coloring composition is spray coated, spin coated, slit coated, roll coated, etc. on a transparent substrate. The coating method is applied so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet rays, which are active energy rays, 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 | stimulate superposition | polymerization of a coloring composition, it can also heat as needed. 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 composition, a water-soluble or alkaline water-soluble resin such as polyvinyl alcohol or water-soluble acrylic resin is applied and dried to form a film that prevents polymerization inhibition by oxygen. Then, ultraviolet exposure can be performed.

  The color filter of the present invention can be produced by an electrodeposition method, a transfer method, etc. in addition to the above method, but the 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.

  The colored composition of the present invention can be used in any of the methods described above, but is most suitable for the photolithography method.

  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. In addition, 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. On the color filter of the present invention, an overcoat film, a columnar spacer, a transparent conductive film, a liquid crystal alignment film, and the like are formed as necessary.

  The color filter is bonded to the counter substrate using a sealant, and after injecting liquid crystal from the injection port provided in the seal part, the injection port is sealed, and if necessary, a polarizing film or a retardation film is placed outside the substrate. A liquid crystal display panel is manufactured by bonding.

  Such liquid crystal display panels include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically convented bend (OCB). It can be used in a liquid crystal display mode in which colorization is performed using a color filter such as the above.

  EXAMPLES The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples unless it exceeds the gist. In the examples and comparative examples, “parts” and “%” mean “parts by weight” and “% by weight”, respectively.

  Also, the identification method of the azo pigment, the acid value of the resin and the resin type dispersant, the weight average molecular weight (Mw) of the resin, the amine value of the resin type dispersant, the quaternary ammonium salt value of the resin type dispersant, The average primary particle diameter of the pigment, the specific surface area of the pigment, and the contrast ratio of the coating film are measured as follows.

<Azo pigment identification method>
The identification of the azo pigment of the present invention is carried out using the MALDI mass spectrometer autoflex III (hereinafter referred to as TOF-MS) manufactured by Bruker Daltonics, and the molecular ion peak of the obtained mass spectrum and the mass number obtained by calculation. Identified with agreement.

<Acid value of resin and resin type dispersant>
The acid value of the resin and the resin-type dispersant was determined by potentiometric titration using a 0.1N potassium hydroxide / ethanol solution. The acid value of the resin and the resin-type dispersant indicates the acid value of the solid content.

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

<Amine value of resin-type dispersant>
The amine value of the resin-type dispersant was determined by potentiometric titration using a 0.1N hydrochloric acid aqueous solution, and then converted to an equivalent of potassium hydroxide. The amine value of the resin-type dispersant indicates the amine value of the solid content.

<Quaternary ammonium salt value of resin-type dispersant>
The quaternary ammonium salt value of the resin-type dispersant was determined by titrating with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted into an equivalent of potassium hydroxide. The quaternary ammonium salt value of the following resin type dispersant indicates the quaternary ammonium salt value of the solid content.

<Average primary particle diameter of pigment>
The average primary particle diameter of the pigment was measured by a method of directly measuring the size of primary particles from an electron micrograph using a transmission (TEM) electron microscope. Specifically, the minor axis diameter and major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the primary pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was obtained by approximating the obtained particle size cube, and the volume average particle size was defined as the average primary particle size.

<Specific surface area of pigment>
The specific surface area of the pigment was measured by an automatic vapor adsorption amount measuring apparatus (“BELSORP18” manufactured by Nippon Bell Co., Ltd.) using the nitrogen adsorption BET method.

<Contrast ratio of coating film>
The light emitted from the backlight unit for liquid crystal display passes through the polarizing plate, is polarized, passes through the dried coating film of the colored composition applied on the glass substrate, and reaches the polarizing plate. If the polarizing planes of the polarizing plate and the polarizing plate are parallel, light is transmitted through the polarizing plate, but if the polarizing plane is perpendicular, the light is blocked by the polarizing plate. However, when the light polarized by the polarizing plate passes through the dried coating film of the colored composition, scattering by the pigment particles occurs, resulting in deviation in a part of the polarization plane. When the amount of light transmitted through the plate is reduced and the polarizing plate is perpendicular, a part of the light is transmitted through the polarizing plate. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) between the luminance when the polarizing plate was parallel and the luminance when it was orthogonal was calculated.
(Contrast ratio) = (Luminance when parallel) / (Luminance when direct)
A color luminance meter ("BM-5A" manufactured by Topcon Corporation) was used as the luminance meter, and a polarizing plate ("NPF-G1220DUN" manufactured by Nitto Denko Corporation) was used as the polarizing plate. In the measurement, a black mask with a 1 cm square hole was applied to the measurement portion in order to block unnecessary light.

First, the used pigment derivative (e) will be described.
<Structural formula of pigment derivative>
Table 1 summarizes the basic skeleton and substituents of the dye derivative (e) used, and appends the structural formula of the derivative.

  Then, the manufacturing method of the acrylic resin solution used for the Example and the comparative example, the resin-type dispersant solution, the refinement | purification pigment, the pigment dispersion, the green photosensitive coloring composition, and the blue photosensitive coloring composition is demonstrated.

<Method for producing acrylic resin solution>
(Adjustment 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, and a stirrer was charged with 70.0 parts of cyclohexanone, heated to 80 ° C., and the inside of the reaction vessel was purged with nitrogen. 13.3 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.4 parts of paracumylphenol ethylene oxide modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), A mixture of 0.4 part of 2,2′-azobisisobutyronitrile was added dropwise over 2 hours. After completion of the dropwise addition, the reaction was continued for 3 hours to obtain an acrylic resin solution having a weight average molecular weight (Mw) of 26000. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content. Propylene glycol monoethyl was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Acrylic resin solution 1 was prepared by adding ether acetate.

(Adjustment of acrylic resin solution 2)
A separable four-necked flask equipped with a thermometer, a cooling pipe, a nitrogen gas introduction pipe, a dropping pipe and a stirring device was charged with 370 parts of cyclohexanone, heated to 80 ° C., and the atmosphere in the flask was replaced with nitrogen. 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2′-azobisisobutyronitrile 2.0 Part of the mixture was added dropwise over 2 hours. After dropping, the reaction was further carried out at 100 ° C. for 3 hours, and then 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was further continued at 100 ° C. for 1 hour. Next, the inside of the container is replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone are put into 9.3 parts of acrylic acid (100% of glycidyl group) and the container is placed at 120 ° C. The reaction was continued for 6 hours, and when the acid value of the solid content reached 0.5, the reaction was terminated to obtain an acrylic resin solution. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain a solution of an acrylic resin having a weight average molecular weight (Mw) of 19000. Obtained. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by weight. Then, an acrylic resin solution 2 which is an active energy ray curable resin was prepared.

<Method for producing resin-type dispersant>
(Resin type dispersant D solution)
A four-necked separable flask equipped with a thermometer, stirrer, distillation tube, and condenser was charged with 70 parts of methyl ethyl ketone, 96.1 parts of n-butyl acrylate, 2.8 parts of sparteine, and 1.9 parts of ethyl bromoisobutyrate. The temperature was raised to 40 ° C. under a nitrogen stream. 1.1 parts of cuprous chloride was added and the temperature was raised to 75 ° C. to initiate polymerization. After polymerization for 3 hours, the polymerization solution is sampled, and it is confirmed that the polymerization yield is 95% or more from the solid content of the polymerization, and 3.9 parts of N, N-dimethylaminoethyl methacrylate and 30.0 parts of methyl ethyl ketone are added. Further, polymerization was performed. After 2 hours, it was confirmed that the polymerization yield was 97% or more from the solid content of the polymerization solution, and the polymerization was stopped by cooling to room temperature. 100 parts of the obtained resin solution was diluted with 100 parts of methyl ethyl ketone, 60 parts of cation exchange resin “Diaion PK228LH (Mitsubishi Chemical Corporation)” was added and stirred at room temperature for 1 hour. Part of "KYOWARD 500SN" (manufactured by Kyowa Chemical Industry Co., Ltd.) was added and stirred for 30 minutes. The polymerization catalyst residue was removed by removing the cation exchange resin and the adsorbent by filtration. Further, the resin solution was concentrated and replaced with ethylene glycol monomethyl ether acetate to obtain a resin type dispersant D solution having an aromatic carboxyl group having an amine value of 76 mgKOH / g and a non-volatile content of 40% by weight per solid content.

<Production method of fine pigment>
(Preparation of refined pigment 1 (PC-1))
Diketopyrrolopyrrole red pigment C.I. I. 200 parts of Pigment Red 254 ("IRGAZIN RED 2030" manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of diketopyrrolopyrrole-based refined pigment 1 (PC-1) was obtained. The specific surface area of the micronized pigment 1 was 70 m ² / g.

(Preparation of refined pigment 2 (PC-2))
Anthraquinone red pigment C.I. I. 200 parts of Pigment Red 177 (“chromophthaled red A2B” manufactured by BASF), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of anthraquinone-based micronized pigment 2 (PC-2) were obtained. The specific surface area of the micronized pigment 2 was 80 m ² / g.

(Preparation of fine pigment 3 (PC-3))
Isoindoline yellow pigment C.I. I. Pigment Yellow 139 ((BASF “Irgafore Yellow 2R-CF”)) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. did. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , 190 parts of refined pigment 3 (PC-3) was obtained. The specific surface area of the micronized pigment 3 was 75 m ² / g.

(Preparation of refined pigment 4 (PC-4))
Nickel complex yellow pigment C.I. I. 200 parts of Pigment Yellow 150 (“E-4GN” manufactured by LANXESS), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is poured into 8 liters of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , 190 parts of yellow refined pigment 4 (PC-4) was obtained. The specific surface area of the micronized pigment 4 was 90 m ² / g.

(Production of refined pigment 5 (PC-5))
Naphthol AS red pigment C.I. I. Pigment Orange 38 (Clariant “NOVOPERM RED HFG”) 100 parts, sodium chloride 1200 parts and diethylene glycol 120 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho), kneaded at 60 ° C. for 6 hours, and salt milling Processed. The obtained kneaded product is poured into 3 liters of warm water, stirred for 1 hour while heating to 70 ° C. to form 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 refined pigment 5 (PC-5) were obtained. The average primary particle size was 70 nm.

(Production of refined pigment 6 (P-1))
63.4 parts of 3-amino-4-methoxybenzanilide are dispersed in 900 parts of water, adjusted to a temperature of 5 ° C. by adding ice, added with 104.0 parts of 35% aqueous hydrochloric acid and stirred for 1 hour, and then added with nitrous acid. An aqueous solution prepared by adding 19.9 parts of sodium to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. On the other hand, 88.4 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C. to prepare a coupler. It was set as the solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.5. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 141 parts of an azo pigment represented by the formula (1-1). . As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment of the formula (1-1).

  Next, 100 parts of the azo pigment of the formula (1-1), 1200 parts of sodium chloride and 120 parts of diethylene glycol are 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. 97 parts of refined pigment 6 (P-1) were obtained. The average primary particle size was 39 nm.

(Production of refined pigment 7 (P-2))
Disperse 43.5 parts of 3-amino-4-methylbenzanilide in 900 parts of water, add ice to adjust the temperature to 5 ° C., add 104.0 parts of 35% aqueous hydrochloric acid, and stir for 1 hour. An aqueous solution prepared by adding 19.9 parts of sodium to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. On the other hand, 88.4 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C. to prepare a coupler. It was set as the solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.2. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 123 parts of an azo pigment represented by the formula (1-2). . As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment of the formula (1-2).

  Next, 100 parts of the azo pigment of formula (1-2), 1200 parts of sodium chloride, and 120 parts of diethylene glycol are 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 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. 97 parts of refined pigment 7 (P-2) were obtained. The average primary particle size was 36 nm.

(Production of refined pigment 8 (P-3))
39.3 parts of 3-amino-4-methylbenzamide are dispersed in 900 parts of water, ice is added to adjust the temperature to 5 ° C., 104.0 parts of 35% aqueous hydrochloric acid is added, and the mixture is stirred for 1 hour, and then sodium nitrite. 19.9 parts was added to 50 parts of water, the prepared aqueous solution was added, and the mixture was stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. On the other hand, 88.4 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C. to prepare a coupler. It was set as the solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.4. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 118 parts of an azo pigment represented by the formula (1-4). . As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment of the formula (1-4).

  Next, 100 parts of the azo pigment of formula (1-4), 1200 parts of sodium chloride, and 120 parts of diethylene glycol are 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 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 refined pigment 8 (P-3) were obtained. The average primary particle size was 38 nm.

(Production of refined pigment 9 (P-4))
Disperse 78.0 parts of the amine compound of the following formula (2-a) in 900 parts of water, add ice to adjust the temperature to 5 ° C., add 104.0 parts of 35% aqueous hydrochloric acid and stir for 1 hour. An aqueous solution prepared by adding 19.9 parts of sodium nitrate to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. On the other hand, 88.4 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C. to prepare a coupler. It was set as the solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.3. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C, filtered, washed with water, and dried at 90 ° C for 24 hours to obtain 138 parts of an azo pigment represented by the formula (1-6) . As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment of the formula (1-6).

  Next, 100 parts of an azo pigment of the formula (1-6), 1200 parts of sodium chloride and 120 parts of diethylene glycol are 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 refined pigment 9 (P-4) were obtained. The average primary particle size was 34 nm.

(Production of refined pigment 10 (P-5))
74.6 parts of the amine compound of the following formula (2-b) was dispersed in 900 parts of water, ice was added to adjust the temperature to 5 ° C., 104.0 parts of 35% hydrochloric acid aqueous solution was added and stirred for 1 hour. An aqueous solution prepared by adding 19.9 parts of sodium nitrate to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. On the other hand, 88.4 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C. to prepare a coupler. It was set as the solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.5. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 145 parts of an azo pigment represented by the formula (1-8). . As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment of the formula (1-8).

  Next, 100 parts of the azo pigment of the formula (1-8), 1200 parts of sodium chloride and 120 parts of diethylene glycol are 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 refined pigment 10 (P-5) were obtained. The average primary particle size was 38 nm.

(Production of refined pigment 11 (P-6))
78.3 parts of the amine compound of the following formula (2-c) is dispersed in 900 parts of water, ice is added to adjust the temperature to 5 ° C., 104.0 parts of 35% aqueous hydrochloric acid solution is added, and the mixture is stirred for 1 hour. An aqueous solution prepared by adding 19.9 parts of sodium nitrate to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. On the other hand, 88.4 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C. to prepare a coupler. It was set as the solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.5. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 146 parts of an azo pigment represented by the formula (1-15). . As a result of mass spectrometry by TOF-MS, it was identified as an azo pigment of the formula (1-15).

  Next, 100 parts of the azo pigment of the formula (1-15), 1200 parts of sodium chloride and 120 parts of diethylene glycol are 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. 96 parts of refined pigment 11 (P-6) were obtained. The average primary particle size was 39 nm.

(Production of fine pigment 12 (P-7))
63.2 parts of the amine compound of the following formula (2-d) is dispersed in 900 parts of water, ice is added to adjust the temperature to 5 ° C., 104.0 parts of 35% aqueous hydrochloric acid solution is added, and the mixture is stirred for 1 hour. An aqueous solution prepared by adding 19.9 parts of sodium nitrate to 50 parts of water was added and stirred for 3 hours. After adding 3.2 parts of sulfamic acid to eliminate excess sodium nitrite, an aqueous solution comprising 192 parts of 80% acetic acid aqueous solution, 210 parts of 25% sodium hydroxide aqueous solution, and 180 parts of water was added, and the diazonium salt aqueous solution was added. did. On the other hand, 88.4 parts of N- [4- (acetylamino) phenyl] -3-hydroxy-2-naphthalenecarboxamide and 174.0 parts of 25% aqueous sodium hydroxide solution were dissolved in 1500 parts of water at 50 ° C. to prepare a coupler. It was set as the solution.
This coupler solution was poured into the 5 ° C. diazonium salt aqueous solution over 30 minutes to carry out a coupling reaction. The pH at this time was 4.7. After stirring for 3 hours and confirming the disappearance of the diazonium salt, the mixture was heated to 70 ° C., filtered, washed with water, and dried at 90 ° C. for 24 hours to obtain 137 parts of an azo pigment represented by the formula (1-17). . As a result of mass spectrometry by TOF-MS, the azo pigment of formula (1-17) was identified.

  Next, 100 parts of the azo pigment of the formula (1-17), 1200 parts of sodium chloride and 120 parts of diethylene glycol are 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 refined pigment 12 (P-7) were obtained. The average primary particle size was 40 nm.

(Preparation of green fine pigment 1)
Phthalocyanine green pigment C.I. I. Pigment Green 58 (Da Nippon Ink Chemical Co., Ltd. “FASTOGEN GREEN A110” 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged in a stainless steel 1 gallon kneader (Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. As a result, 190 parts of the green refined pigment 1 was obtained, and the specific surface area of the green refined pigment 1 was 75 m ² / g.

(Preparation of blue refined pigment 1)
Phthalocyanine blue pigment C.I. I. Pigment Blue 15: 6 (Toyo Ink Mfg. Co., Ltd. “LIONOL BLUE ES”, specific surface area 60 m 2 / g) 200 parts, sodium chloride 1400 parts and diethylene glycol 360 parts were charged into a stainless steel 1 gallon kneader (Inoue Seisakusho). It knead | mixed at 80 degreeC for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. 190 parts of blue refined pigment 1 were obtained. The specific surface area of the blue refined pigment 1 was 80 m ² / g.

(Preparation of purple fine pigment 1)
Dioxazine-based purple pigment C.I. I. 200 parts of Pigment Violet 23 (“LIONOGEN VIOLET RL” manufactured by Toyo Ink Manufacturing Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1 gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, the kneaded product is put into 8000 parts of warm water, stirred for 2 hours while heating to 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85 ° C. overnight. , 190 parts of purple refined pigment 1 was obtained. The specific surface area of the purple refined pigment 1 was 95 m ² / g.

<Method for producing pigment dispersion>
(Pigment dispersion (DC-1))
The following mixture 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) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-1) whose non-volatile component is 20 weight% was produced.

Fine pigment 1 (PC-1): 11.0 parts (CI Pigment Red 254)
Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin-type dispersant solution (dispersant A): 5.0 parts

(Pigment dispersion (DC-2))
The following mixture 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) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-2) whose non-volatile component is 20 weight% was produced.

Fine pigment 2 (PC-2): 11.0 parts (CI Pigment Red 177)
Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin-type dispersant solution (dispersant A): 5.0 parts

(Pigment dispersion (DC-3))
The following mixture 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) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-3) whose non-volatile component is 20 weight% was produced.

Fine pigment 3 (PC-3): 11.0 parts (CI Pigment Yellow 139)
Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin-type dispersant solution (dispersant A): 5.0 parts

(Pigment dispersion (DC-4))
The following mixture 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) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (DC-4) whose non-volatile component is 20 weight% was produced.

Fine pigment 4 (PC-4): 11.0 parts (CI Pigment Yellow 150)
Acrylic resin solution 1: 35.0 parts Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts Resin type dispersant solution (“EFKA4300” manufactured by BASF): 5.0 parts

<Green photosensitive coloring composition, blue photosensitive coloring composition production method>
(Green photosensitive coloring composition 1)
The following mixture 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) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The green pigment dispersion 1 having a nonvolatile content of 20% by weight was prepared.

Green refined pigment 1 (CI Pigment Green 58): 11.0 parts acrylic resin solution 1: 35.0 parts propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts resin type dispersant solution (manufactured by BASF) "EFKA4300"): 5.0 parts

Subsequently, 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 green photosensitive coloring composition 1.

Green pigment dispersion 1: 32.0 parts Pigment dispersion (DC-4): 18.0 parts Acrylic resin solution 2: 7.5 parts Photopolymerizable monomer (“Aronix M-402” manufactured by Toagosei Co., Ltd.) : 2.0 parts dipentaerythritol hexaacrylate photoinitiator ("OXE-02" manufactured by BASF): 1.5 parts ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole -3-yl]-, 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

(Blue photosensitive coloring composition 1)
The non-volatile content is the same as that of Green Pigment Dispersion 1 except that Green Refined Pigment 1 (CI Pigment Green 58) is changed to Blue Refined Pigment 1 (CI Pigment Blue 15: 6). 20% by weight of blue pigment dispersion 1 was obtained.

  The non-volatile content is 20 weights in the same manner as the green pigment dispersion 1 except that the green refined pigment 1 (CI Pigment Green 58) is changed to the purple refined pigment 1 (CI Pigment Violet 23). % Purple pigment dispersion 1 was obtained.

  Subsequently, 32.0 parts of the green pigment dispersion 1, 18.0 parts of the pigment dispersion (DC-4), 50.0 parts in total, 46.0 parts of the blue dispersion 1, and 4. 4 parts of the purple dispersion 1. A blue photosensitive coloring composition 1 was obtained in the same manner as the green photosensitive coloring composition 1 except that 0 part was replaced with a total of 50.0 parts.

[Example 1]
(Pigment dispersion (D-1))
The following mixture 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) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. The pigment dispersion (D-1) whose non-volatile component is 20 weight% was produced.

Fine pigment 6 (P-1): 10.0 parts Derivative (derivative A): 1.0 part Acrylic resin solution 1: 35.0 parts Resin-type dispersant solution (resin-type dispersant A): 5.0 parts "DISPERBYK2000" (by Big Chemie Japan)
Non-volatile content: 40% by weight Propylene glycol monomethyl ether acetate / butoxyethanol solution Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

[Examples 2 to 20]
(Pigment dispersion (D-2 to 20, 22))
Hereinafter, the pigment dispersion (D-1) was prepared in the same manner as the pigment dispersion (D-1) except that the pigment, derivative, resin-type dispersant solution and solvent were changed to the composition shown in Table 3 and the blending amount (parts by weight). -2 to 20, 22) were adjusted.

[Example 21]
(Pigment dispersion (D-21))
The following mixture 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) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a pigment dispersion (D-21) was produced.

Finer pigment 6 (P-1): 11.0 parts acrylic resin solution 1: 35.0 parts resin type dispersant solution (resin type dispersant A): 5.0 parts “DISPERBYK2000” (manufactured by Big Chemie Japan)
Non-volatile content: 40% by weight Propylene glycol monomethyl ether acetate / butoxyethanol solution Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

[Comparative Example 1]
(Pigment dispersion (D-22))
The following mixture was stirred and mixed so as to be uniform, then dispersed with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan) using zirconia beads having a diameter of 0.5 mm, and then 5.0 μm. And a pigment dispersion (D-22) was produced.

Fine pigment 6 (P-1): 10.0 parts Acrylic resin solution 1: 40.0 parts Derivative (derivative A): 1.0 part Propylene glycol monomethyl ether acetate (PGMAC): 49.0 parts

[Comparative Example 2]
(Pigment dispersion (D-23))
Hereinafter, a pigment dispersion (D-1) was prepared in the same manner as in the pigment dispersion (D-1) except that the pigment, derivative, resin-type dispersant solution, and solvent were changed to the composition shown in Table 2 and the blending amount (parts by weight). D-23 was adjusted.

Abbreviations in Table 3 are described below.
Resin Type Dispersant A: DISPERBYK2000 (produced by Big Chemie Japan) Nonvolatile content 40% by weight Propylene glycol monomethyl ether acetate / butoxyethanol solution Resin type dispersant B: BYK-LPN6919 (produced by Big Chemie Japan) Nonvolatile content 60% by weight propylene Glycol monomethyl ether acetate / ethanol solution resin-type dispersant C: SOLPERSE 76500 (manufactured by Lubrizol) Non-volatile content 50% by weight butyl acetate solution

[Evaluation of Colored Composition for Color Filter (Pigment Dispersion)]
The viscosity characteristics, color characteristics, and contrast ratio of the pigment dispersions (D-1 to 23) obtained in Examples and Comparative Examples were evaluated by the following methods. Table 4 shows the evaluation results.

<Viscosity characteristics>
As for the viscosity of the pigment dispersion, an initial viscosity at 25 ° C. was measured using an E type viscometer (“ELD type viscometer” manufactured by Toki Sangyo Co., Ltd.). Separately, 25 g of the pigment dispersion was allowed to stand at 40 ° C. for 24 hours in a sealed state in a glass container, and then the viscosity was measured by the same method as described above to obtain the time-dependent viscosity.

<Color characteristic evaluation>
The obtained photosensitive coloring composition is applied onto a glass substrate, dried at 70 ° C. for 20 minutes, and further heated at 230 ° C. for 60 minutes, so that the chromaticity of the substrate is x = 0. A coated substrate was obtained such that 640, y = 0.322. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

<Contrast ratio (CR)>
Using the obtained pigment dispersion, a spin coater was used to produce three coated substrates so that the dry film thickness was about 1 μm by changing the number of rotations. After coating, the film was dried in a hot air oven at 80 ° C. for 30 minutes, and the film thickness and the contrast ratio were measured. The contrast ratio (CR) at a film thickness of 1 μm was determined from the three points of data by the primary correlation method.

  The color of the present invention comprising a colorant (a) containing a naphtholazo pigment (a1) represented by the general formula (1) and a resinous dispersant (c) which is a resinous dispersant having a basic substituent. The colored composition for filter obtained the result that viscosity was low with respect to the colored composition of a comparative example, and brightness and CR were high.

In particular, the phthalazo pigment (a1) is an existing pigment, C.I. I. Compared to Pigment Orange 38, C.I. I. Pigment Red 254, bluer, C.I. I. It is yellowish than CI Pigment Red 177, and the rising wavelength of the transmission spectrum is in the range of 570 to 590 nm. Therefore, it effectively acts on the bright line of the backlight generally used in liquid crystal display devices, and high brightness is obtained. It was. Further, by using the naphtholazo pigment (a1) and the resin-type dispersant (c) in combination, the pigment can stably exist in the state of primary particles, and a high contrast ratio can be obtained at the same time.
In particular, when A in the general formula (1) is a phenyl group which may have a substituent, superiority was observed in brightness and CR.

  Furthermore, when the pigment derivative (e), particularly the pigment derivative having an acidic substituent, was included, the viscosity was lower and the CR was higher.

[Example 22]
(Photosensitive coloring composition (R-1))
The following mixture (100 parts in total) was stirred and mixed so as to be uniform, and then filtered through a 1.0 μm filter to obtain a photosensitive colored composition (R-1).

(Pigment dispersion) (Total 50 parts)
Pigment dispersion (D-1): 25.0 parts Pigment dispersion (DC-1): 15.0 parts Pigment dispersion (DC-2): 10.0 parts Acrylic resin solution 2: 7.5 parts Photopolymerization (Aronix M-402 manufactured by Toagosei Co., Ltd.): 2.0 parts dipentaerythritol hexaacrylate photopolymerization initiator; (“OXE-02” manufactured by BASF): 1.5 parts Etanone, 1 -[9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime)
Cyclohexanone: 39.0 parts

[Examples 23 to 46, Comparative Examples 3 to 5]
(Photosensitive coloring composition (R-2 to 28))
The photosensitive colored composition (R-2) was the same as the photosensitive colored composition (R-1) except that the pigment dispersion was changed to the type of pigment dispersion shown in Table 5 and the blending amount (parts by weight). To 28). In adjusting each photosensitive coloring composition, all were added so that the total of the pigment dispersion was 50 parts, and 100 parts of the photosensitive coloring composition was adjusted.

[Evaluation of Color Filter Coloring Composition (Photosensitive Coloring Composition)]
The color characteristics of the photosensitive coloring compositions (R-1 to 28) obtained in Examples and Comparative Examples (R-1 to 28), the contrast ratio, and the heat resistance of the coating film were evaluated by the following methods. Table 6 shows the evaluation results.

<Color characteristic evaluation>
The obtained photosensitive coloring composition is applied onto a glass substrate, dried at 70 ° C. for 20 minutes, and further heated at 230 ° C. for 60 minutes, so that the chromaticity of the substrate is x = 0. 658, y = 0.325 was obtained. The brightness (Y) of the obtained substrate was measured with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optical Co., Ltd.).

<Contrast ratio (CR)>
Using the obtained photosensitive coloring composition, a three-point coated substrate was prepared using a spin coater so that the number of revolutions was changed and the dry film thickness was about 1 μm. After coating, the film was dried in a hot air oven at 80 ° C. for 30 minutes, and the film thickness and the contrast ratio were measured. The contrast ratio (CR) at a film thickness of 1 μm was determined from the three points of data by the primary correlation method.

<Evaluation of heat resistance of coating film>
The photosensitive coloring composition was applied on a transparent substrate so that the dried coating film was about 2.0 μm, and dried at 70 ° C. for 20 minutes. After performing ultraviolet exposure through a mask having a predetermined pattern, an alkali developer was sprayed by spraying to remove the uncured portion, thereby forming a desired pattern. Then, after heating and cooling in an oven at 230 ° C. for 1 hour, the obtained coating film was subjected to L * a * b * color system using a C light source with a microspectrophotometer (“OSP-SP200” manufactured by Olympus Optics) The color measurement (L * (1), a * (1), b * (1)) was performed. After that, as a heat resistance test, it was heated in an oven at 250 ° C. for 1 hour, and color measurement (L * (2), a * (2), b * (2)) was similarly performed. It calculated and the heat resistance of the coating film was evaluated in the following four steps.
ΔEab * = √ ((L * (2) -L * (1)) ² + (a * (2)-a * (1)) ² + (b * (2)-b * (1)) ² )
A: ΔEab * is less than 1.5 ○: ΔEab * is 1.5 or more and less than 3.0
Δ: ΔEab * is 3.0 or more and less than 5.0 ×: ΔEab * is 5.0 or more

  The color composition for color filter of the present invention comprising the naphtholazo pigment (a1) represented by the general formula (1) and the resin-type dispersant (c) having a basic substituent has both brightness and CR. High and heat resistance was good.

  Further, the photosensitive coloring composition containing the pigment derivative having an acidic substituent further had better CR than the photosensitive coloring composition not containing the pigment derivative.

  On the other hand, the photosensitive coloring composition containing no naphthol azo pigment (a1) had poor heat resistance and low brightness.

[Production example of color filter]
Using the photosensitive coloring composition (R-1) of the present invention, the green photosensitive coloring composition 1 and the blue photosensitive coloring composition 1, the dry film thickness was 1.7 μm by spin coating on the substrate. It is applied so that it is dried, exposed to ultraviolet light through a mask having a predetermined pattern provided in a non-contact state with the coating film, and then an alkali developer is sprayed by spraying to remove the uncured portion and After forming the pattern, it was heated at 230 ° C. for 1 hour. By repeating the same operation for green and blue to produce a color filter, an RGB three-color filter having high brightness and excellent heat resistance could be produced.

Claims (7)

In the coloring composition containing the colorant (a), the resin (b), the resin-type dispersant (c), and the solvent (d), the colorant (a) is represented by the following general formula (1). A red coloring composition for a color filter, comprising the naphtholazo pigment (a1) shown, wherein the resin-type dispersant (c) is a resin-type dispersant having a basic substituent.

[In General Formula (1), A represents a hydrogen atom, a benzimidazolone group, a phenyl group which may have a substituent, or a heterocyclic group which may have a substituent.
R ¹ represents a hydrogen atom, a halogen atom, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁷ , or —COOR ⁸ . R ^{2 to} R ⁶ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a trifluoromethyl group, an alkyl group having 1 to 4 carbon atoms, —OR ⁹ , —COOR ¹⁰ , —CONHR ¹¹ , or an _-SO 2 ^{NHR 12.} R ^{7 to} R ¹² each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms.
However, it excludes when A and R ^{2 to} R ⁶ are a hydrogen atom and R ¹ is a halogen atom. ]   The red coloring composition for a color filter according to claim 1, wherein A is a phenyl group which may have a substituent.   The red coloring composition for a color filter according to claim 1 or 2, wherein the resin-type dispersant (c) has a basic substituent containing a nitrogen atom.   Furthermore, the dye derivative (e) is included, and the dye derivative (e) is at least selected from the group consisting of a pigment derivative having an acidic substituent, a β-naphthol derivative having an acidic substituent, and a triazine derivative having an acidic substituent. The red coloring composition for a color filter according to any one of claims 1 to 3, comprising a pigment derivative having one kind of acidic substituent.   The colorant (a) further contains C.I. I. Pigment red 254, C.I. I. Pigment red 177, C.I. I. Pigment yellow 139 and C.I. I. The red coloring composition for a color filter according to any one of claims 1 to 4, comprising at least one pigment selected from the group consisting of CI Pigment Yellow 150.   Furthermore, the red coloring composition for color filters of any one of Claims 1-5 containing a photopolymerizable monomer and / or a photoinitiator.   A color filter comprising a red filter segment formed from the red coloring composition for a color filter according to any one of claims 1 to 6 on a substrate.