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

Abstract

To provide a color filter coloring composition which offers superior heat resistance, less foreign matter in a coating, good storage stability, solvent resistance, and dye transferability, as well as high brightness and contrast, and to provide a color filter.SOLUTION: The above challenge is cleared by using a color filter colorant containing an azo pigment consisting of a compound represented by a general formula (3), where content of the azo pigment is 20-80 mass% with respect to 100 mass% of a total colorant.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a colorant for color filters used in the production of color filters for use in color liquid crystal displays, color solid-state image pickup devices, and the like, a colorant composition, and a color filter formed using the same. [Background technology]

[0002] Liquid crystal display devices are displays in which a liquid crystal layer sandwiched between two polarizing plates controls the degree of polarization of light that passes through the first polarizing plate, and controls the amount of light that passes through the second polarizing plate to display an image, and the most common type uses twisted nematic (TN) liquid crystals. Other representative liquid crystal display types include the in-plane switching (IPS) type, in which a pair of electrodes is provided on one of the substrates and an electric field is applied in a direction parallel to the substrate, the vertical alignment (VA) type, in which nematic liquid crystals with negative dielectric anisotropy are vertically aligned, and the optically concave bend (OCB) type, in which the optical axes of uniaxial retardation films are mutually orthogonalized to provide optical compensation, and all of these types are in practical use.

[0003] Liquid crystal display devices are capable of displaying color by placing a color filter between two polarizing plates. In recent years, as these devices have come to be used in televisions, personal computer monitors, and other applications, there has been an increasing demand for color filters with higher contrast and brightness.

[0004] A color filter is made up of fine stripe-shaped filter segments of two or more different hues arranged in parallel or crossing on the surface of a transparent substrate such as glass, or fine filter segments arranged in a fixed array vertically and horizontally. The filter segments are very fine, ranging from a few microns to a few hundred microns, and are arranged in a regular pattern according to the hue.

[0005] Generally, in color liquid crystal display devices, transparent electrodes for driving liquid crystals are formed on color filters by deposition or sputtering, and an alignment film for aligning the liquid crystals in a certain direction is formed on top of the transparent electrodes. To obtain sufficient performance from these transparent electrodes and alignment films, they must be formed at high temperatures, generally above 200°C, and preferably above 230°C. For this reason, the current mainstream method for manufacturing color filters is a method called the pigment dispersion method, which uses a pigment with excellent light resistance and heat resistance as a colorant.

[0006] The quality items required for color filters include brightness and contrast ratio. If a color filter with a low contrast ratio is used, it will disrupt the degree of polarization controlled by the liquid crystal, causing light to leak when it should be blocked (OFF state) and attenuating the transmitted light when it should be transmitted (ON state), resulting in a blurred screen. For this reason, high contrast is essential to realizing a high-quality liquid crystal display device.

[0007] In addition, when a low-luminance color filter is used, the light transmittance is low, resulting in a dark screen, and in order to make the screen brighter, it is necessary to increase the number of backlights, which are light sources. Therefore, from the viewpoint of suppressing increases in power consumption, there is a trend toward higher luminance color filters. Furthermore, as mentioned above, as color liquid crystal devices have come to be used in televisions, computer monitors, etc., there is an increasing demand for color filters with higher luminance, higher contrast, and higher reliability.

[0008] For the red filter segment, which is one of the three primary colors (red, green, and blue; RGB) of a color filter substrate, pigments with excellent light and heat resistance, such as diketopyrrolopyrrole pigments, anthraquinone pigments, or perylene pigments, are generally used alone or in combination as colorants.

[0009] Among the above pigment types, CI Pigment Red 254, a diketopyrrolopyrrole pigment, and CI Pigment Red 177, an anthraquinone pigment, are used as main pigments from the viewpoint of brightness, and from the viewpoint of contrast ratio, respectively. Among these, CI Pigment Red 177 has a lower spectral transmittance than CI Pigment Red 254 and a poor spectral shape, and therefore has the drawback of causing a decrease in brightness as CI Pigment Red 177 is added. Therefore, there is a demand for the development of a substitute material for CI Pigment Red 177 that has excellent brightness.

[0010] In recent years, in order to realize high brightness and high coloring power, it has been proposed to use azo pigments such as CI Pigment Red 269 and disazo pigments described in Patent Document 3 as main pigments, but since the affinity of the pigment to the solvent and the acidity of the pigment surface are different from those of CI Pigment Red 254 and CI Pigment Red 177, they have disadvantages such as inferior dispersibility, fluidity, and storage stability, as well as inferior heat resistance and light resistance, and no practical color filter has been obtained. In addition, with azo pigments such as CI Pigment Red 269, there is a problem of reduced brightness due to color transfer to adjacent filter segments of other colors, and there is a high demand for migration properties.

[0011] Patent Documents 1 to 4 propose using CI Pigment Red 177, CI Pigment Red 269, and the disazo pigments described in Patent Documents 3 and 4 as main pigments in order to further improve the brightness of the red filter segment. However, sufficient brightness and storage stability could not be obtained, and further improvements were required. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] JP 2008-304521 A [Patent Document 2] Special Publication No. 2007-533802 [Patent Document 3] JP 2014-160160 A [Patent Document 4] Patent No. 6368844 Summary of the Invention [Problem to be solved by the invention]

[0013] An object of the present invention is to provide a coloring composition for color filters which not only has excellent heat resistance, little coating foreign matter, good storage stability, solvent resistance and dye migration properties, but also has high brightness and contrast. [Means for solving the problem]

[0014] As a result of extensive investigations, the present inventors have found that the above problems can be solved by using an azo pigment having a specific structure as a colorant for a color filter, and have arrived at the present invention.

[0015] That is, the present invention relates to an azo pigment which is any of the compounds represented by the following general formulas (1) to (3). General formula (1) [ka] [In general formula (1), R 1 ~R 5 each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, -CONR 6 R 7 OR -SO 2 NR 8 R 9 Represents R 6 ~R 9 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. 1 , R 3 and R 4Except when all are hydrogen atoms. X 1 ~X 4 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, or a halogen atom. General formula (2) [ka] [In general formula (2), R 10 ~R 14 each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, -CONR 15 R 16 OR -SO 2 NR 17 R 18 Represents R 15 ~R 18 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. 10 , R 12 and R 13 Except when all are hydrogen atoms. X 5 ~X 12 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, or a halogen atom. A represents a direct bond, an alkylene group which may have a substituent, -O-, -S-, -CO-, -SO 2 -, -COO-, -CONH-, or -SO 2 It stands for NH-. General formula (3) [ka] [In general formula (3), R 19 ~R23 each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, -CONR 24 R 25 OR -SO 2 NR 26 R 27 Represents R 24 ~R 27 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. 19 , R 21 and R 22 Except when all are hydrogen atoms.

[0016] In addition, an embodiment of the present invention is R 1 ~R 5、 R in the above general formula (2) 10 ~R 14、 and R in the general formula (3) 19 ~R 23 At least one of -CONHY or -SO 2 The present invention relates to the azo pigment, characterized in that the azo pigment is NHY (wherein Y represents a phenyl group which may have a substituent).

[0017] The present invention also relates to a colorant for color filters, which contains the azo pigment.

[0018] The present invention also relates to a coloring composition for color filters, comprising a colorant and a binder resin, wherein the colorant is the colorant for color filters described above.

[0019] The present invention also relates to the coloring composition for color filters, further comprising a resin-type dispersant having an acidic substituent.

[0020] The present invention also relates to the coloring composition for color filters, wherein the resin type dispersant having an acidic substituent is a resin type dispersant having an aromatic carboxyl group.

[0021] The present invention also relates to the coloring composition for color filters, further comprising a dye derivative, the dye derivative having a basic substituent.

[0022] The present invention also relates to the coloring composition for color filters, wherein the colorant further comprises at least one selected from the group consisting of CI Pigment Red 242, CI Pigment Red 254, CI Pigment Red 291, CI Pigment Yellow 138, CI Pigment Yellow 139, CI Pigment Yellow 150, and a yellow pigment represented by the following general formula (4): General formula (4) [ka] [In general formula (4), Z 1 ~Z 13 each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryl group which may have a substituent, -SO 3 It represents H, -COOH, and monovalent to trivalent metal salts of these acidic groups, alkylammonium salts, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. Z 1 ~Z 4 and / or Z 10 ~Z 13 Adjacent groups may be joined together to form an aromatic ring which may have a substituent.

[0023] The present invention also relates to the coloring composition for color filters, further comprising a photopolymerizable monomer.

[0024] The present invention also relates to a color filter comprising a substrate and a filter segment formed from the coloring composition for color filters. Effect of the Invention

[0025] According to the present invention, there is an excellent effect that a coloring composition for color filters and a color filter which are excellent in heat resistance, have little coating foreign matter, have good storage stability, solvent resistance and dye migration properties, and also have high brightness and contrast can be provided. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0026] The present invention will be described in detail below. In this specification, unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" refer to "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively. In addition, "CI" in this specification means Color Index (CI).

[0027] <Azo pigments> First, the azo pigments of the present invention represented by the general formulas (1) to (3) will be described. In the present specification, the "azo pigments of the general formulas (1) to (3)" and the "colorant for color filters" are sometimes abbreviated as "pigment" and "colorant", respectively.

[0028] General formula (1) [ka] [In general formula (1), R 1 ~R 5each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, -CONR 6 R 7 OR -SO 2 NR 8 R 9 Represents R 6 ~R 9 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. 1 , R 3 and R 4 Except when all are hydrogen atoms. X 1 ~X 4 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, or a halogen atom.

[0029] R 1 ~R 5 In the above, examples of the "halogen atom" include fluorine, bromine, chlorine, and iodine, and among these, chlorine is preferred.

[0030] R 1 ~R 5 In the above, examples of the "alkyl group which may have a substituent" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, a tert-amyl group, a 2-ethylhexyl group, a stearyl group, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a 2-chloroethyl group, a 2-nitroethyl group, a cyclopentyl group, a cyclohexyl group, a dimethylcyclohexyl group, and the like. Among these, a methyl group and a trifluoromethyl group are preferable.

[0031] R 1 ~R 5In the above, examples of the "alkoxy group which may have a substituent" include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, a 2-ethylhexyloxy group, a trifluoromethoxy group, a cyclohexyloxy group, a stearyloxy group, and a 2-(diethylamino)ethoxy group. Of these, a methoxy group and a trifluoromethoxy group are preferred, and a methoxy group is particularly preferred.

[0032] R 1 ~R 5 In the above, examples of the "aryloxy group which may have a substituent" include a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group, a 4-chloro-2-methylphenyloxy group, a 4-tert-butylphenyloxy group, a 4-methoxyphenyloxy group, a 4-diethylaminophenyloxy group, a 4-nitrophenyloxy group, and the like. Of these, a phenoxy group is preferable.

[0033] R 6 ~R 9 In the above, examples of the "alkyl group which may have a substituent" include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, a tert-amyl group, a 2-ethylhexyl group, a stearyl group, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a 2-hydroxyethyl group, a 2-chloroethyl group, a 2-nitroethyl group, a cyclopentyl group, a cyclohexyl group, a dimethylcyclohexyl group, and the like. Preferred are an isopropyl group, an n-butyl group, a tert-butyl group, an isobutyl group, and a 2-hydroxyethyl group.

[0034] R 6 ~R 9 In the formula (I), the substituent of the "phenyl group which may have a substituent" is R 1 ~R 5Examples of the alkyl group include a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, and an aryloxy group which may have a substituent in the above formula (I), and in addition thereto, a hydroxyl group, an amino group, -NR 101 R 102 , sulfo group, -SO 2 NR 103 R 104 , -COOR 105 , -CONR 106 R 107 , a nitro group, and a cyano group. R 101 ~R 107 each independently represents a hydrogen atom or an alkyl group which may have a substituent, and the "alkyl group which may have a substituent" is preferably an alkyl group substituted with an amino group, a monoalkylamino group, or a dialkylamino group.

[0035] X 1 ~X 4 In the above, the "alkyl group which may have a substituent" is R 1 ~R 5 It is synonymous with that in.

[0036] X 1 ~X 4 In the above, the "alkoxy group which may have a substituent" is R 1 ~R 5 It is synonymous with that in.

[0037] General formula (2) [ka] [In general formula (2), R 10 ~R 14 each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, -CONR 15 R 16 OR -SO 2 NR 17 R18 Represents R 15 ~R 18 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. 10 , R 12 and R 13 Except when all are hydrogen atoms. X 5 ~X 12 each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, or a halogen atom. A represents a direct bond or a divalent linking group. Examples of the divalent linking group include an alkylene group which may have a substituent, -O-, -S-, -CO-, -SO 2 -, -COO-, -CONH-, -SO 2 It stands for NH-.

[0038] R 10 ~R 14 In the above, the "halogen atom", "optionally substituted alkyl group", "optionally substituted alkoxy group", and "optionally substituted aryloxy group" are R 1 ~R 5 It is synonymous with that in.

[0039] R 15 ~R 18 In the above, the "optionally substituted alkyl group" and the "optionally substituted phenyl group" are R 6 ~R 9 It is synonymous with that in.

[0040] X 5 ~X 12 In the above, the "alkyl group which may have a substituent" and the "alkoxy group which may have a substituent" are R 1 ~R 5 It is synonymous with that in.

[0041] In A, examples of the alkylene group which may have a substituent include a methylene group, an ethylene group, an n-propylene group, an n-butylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, and an n-dodecylene group. Examples of the substituent include R 1 ~R 5 Examples of the alkyl group that may have a substituent include an alkyl group represented by the following formula:

[0042] A in the general formula (2) is an alkylene group which may have a substituent, -O-, -S-, -CO-, -SO 2 - is preferred, among which -SO 2 is particularly preferred.

[0043] General formula (3) [ka] [In general formula (3), R 19 ~R 23 each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, -CONR 24 R 25 OR -SO 2 NR 26 R 27 Represents R 24 ~R 27 each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. 19 , R 21 and R 22 Except when all are hydrogen atoms.

[0044] R 19 ~R 23 In the above, the "halogen atom", "optionally substituted alkyl group", "optionally substituted alkoxy group", and "optionally substituted aryloxy group" are R 1 ~R 5 It is synonymous with that in.

[0045] R 24 ~R 27 In the above, the "optionally substituted alkyl group" and the "optionally substituted phenyl group" are R 6 ~R 9 It is synonymous with that in.

[0046] In addition, R in the general formula (1) 1 ~R 5、 R in general formula (2) 10 ~R 14、 and R in general formula (3) 19 ~R 23 At least one of -CONHY or -SO 2 NHY (Y represents a phenyl group which may have a substituent) is preferred from the viewpoint of storage stability.

[0047] <Colorants for color filters> The colorant for color filters of the present invention is characterized by containing an azo pigment consisting of a compound represented by the general formulas (1) to (3). The colorant for color filters of the present invention may be used in combination with other colorants such as pigments or dyes other than the pigment consisting of the compound represented by the general formulas (1) to (3) above, in order to adjust the chromaticity, etc., within the scope of not impairing the effects of the present invention. These pigments and dyes may be used alone, or two or more kinds may be mixed in any ratio as necessary.

[0048] Other colorants include red pigments such as, for example, CI Pigment Red 7, 14, 41, 48:1, 48:2, 48:3, 48:4, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 122, 146, 168, 169, 176, 177, 178, 179, 184, 185, 187, 200, 202, 208, 210, 242, 246, 254, 255, 264, 269, 270, 272, 273, 274, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295 or 296. Examples of red dyes include xanthene dyes, azo dyes (pyridone-based, barbituric acid-based, etc.), disazo dyes, anthraquinone dyes, methine dyes, etc. Furthermore, the dyes may be in the form of lake pigments obtained by making these dyes into lakes, inorganic salts of acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acid dyes and nitrogen-containing compounds, sulfonic acid amide compounds of acid dyes, etc.

[0049] Also, orange pigments such as CI Pigment Orange 43, 71, or 73 and / or CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29 5, 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, 13 9, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, or a yellow pigment represented by the following general formula (4) can be used in combination. In addition, examples of orange dyes and / or yellow dyes include quinoline-based, azo-based (pyridone-based, barbituric acid-based, metal complex-based, etc.), disazo-based, methine-based, etc.

[0050] From the viewpoints of fastness such as heat resistance and light resistance and chromaticity range, preferred colorants to be used in combination include azo-based, diketopyrrolopyrrole-based, anthraquinone-based, quinophthalone-based, and perylene-based pigments.Specific examples include CI Pigment Red 177, 242, 254, 269, 291, 295, and 296, CI Pigment Yellow 138, 139, 150, and 185, and yellow pigments represented by the following general formula (4). Particularly from the viewpoint of brightness and coloring power, CI Pigment Red 242, 254, 291, CI Pigment Yellow 138, 139, 150, and the yellow pigment represented by the following general formula (4) are more preferable.

[0051] General formula (4) [ka] [In general formula (4), Z 1 ~Z 13 each independently represents a hydrogen atom, a halogen atom, or a substituent an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, -SO 3 It represents H, -COOH, and monovalent to trivalent metal salts of these acidic groups, alkylammonium salts, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. Z 1 ~Z 4 and / or Z 10 ~Z 13 Adjacent groups may be joined together to form an aromatic ring which may have a substituent.

[0052] Here, examples of the halogen atom include fluorine, chlorine, bromine and iodine atoms.

[0053] Examples of the alkyl group which may have a substituent include linear or branched alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a neopentyl group, an n-hexyl group, an n-octyl group, a stearyl group, and a 2-ethylhexyl group, as well as alkyl groups having a substituent such as a trichloromethyl group, a trifluoromethyl group, a 2,2,2-trifluoroethyl group, a 2,2-dibromoethyl group, a 2,2,3,3-tetrafluoropropyl group, a 2-ethoxyethyl group, a 2-butoxyethyl group, a 2-nitropropyl group, a benzyl group, a 4-methylbenzyl group, a 4-tert-butylbenzyl group, a 4-methoxybenzyl group, a 4-nitrobenzyl group, and a 2,4-dichlorobenzyl group.

[0054] Examples of alkoxyl groups which may have a substituent include linear or branched alkoxyl groups such as methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutyloxy, tert-butyloxy, neopentyloxy, 2,3-dimethyl-3-pentoxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy groups, as well as alkoxyl groups having a substituent such as trichloromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 2,2,3,3-tetrafluoropropyloxy, 2,2-ditrifluoromethylpropoxy, 2-ethoxyethoxy, 2-butoxyethoxy, 2-nitropropoxy, and benzyloxy groups.

[0055] Examples of the aryl group which may have a substituent include aryl groups such as a phenyl group, a naphthyl group, and an anthranyl group, as well as aryl groups having a substituent such as a p-methylphenyl group, a p-bromophenyl group, a p-nitrophenyl group, a p-methoxyphenyl group, a 2,4-dichlorophenyl group, a pentafluorophenyl group, a 2-aminophenyl group, a 2-methyl-4-chlorophenyl group, a 4-hydroxy-1-naphthyl group, a 6-methyl-2-naphthyl group, a 4,5,8-trichloro-2-naphthyl group, an anthraquinonyl group, and a 2-aminoanthraquinonyl group.

[0056] The acidic group is -SO 3 Examples of the monovalent to trivalent metal salts of these acidic groups include sodium salts, potassium salts, magnesium salts, calcium salts, iron salts, aluminum salts, etc. Examples of the alkyl ammonium salts of acidic groups include ammonium salts of long-chain monoalkylamines such as octylamine, laurylamine, and stearylamine, and quaternary alkyl ammonium salts such as palmityl trimethyl ammonium, dilauryl dimethyl ammonium, and distearyl dimethyl ammonium salts.

[0057] A phthalimidomethyl group (C 6 H 4 (CO)2 N-CH 2 -), and a sulfamoyl group (H 2 NSO 2 Examples of the "substituent" in -) include the above-mentioned halogen atoms, alkyl groups which may have a substituent, alkoxyl groups which may have a substituent, and aryl groups which may have a substituent.

[0058] Z in general formula (4) 1 ~Z 4 and / or Z 10 ~Z 13 Adjacent groups of are taken together The aromatic ring may be a hydrocarbon aromatic ring or a heteroaromatic ring, and examples of the hydrocarbon aromatic ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring, and examples of the heteroaromatic ring include a pyridine ring, a pyrazine ring, a pyrrole ring, a quinoline ring, a quinoxaline ring, a furan ring, a benzofuran ring, a thiophene ring, a benzothiophene ring, an oxazole ring, a thiazole ring, an imidazole ring, a pyrazole ring, an indole ring, and a carbazole ring.

[0059] Specific examples of the yellow pigment represented by formula (4) used in the colorant for color filters of the present invention include the following quinophthalone compounds (a) to (r), but the present invention is not limited thereto. The quinophthalone compound used in the present invention can be produced, for example, by the method described in Japanese Patent Publication No. 2930774, but the present invention is not limited thereto.

[0060] [ka] JPEG0007632708000010.jpg111142

[0061] [ka] JPEG0007632708000012.jpg113134

[0062] [ka]

[0063] Dyes that can be used in combination are preferably those that exhibit a red or purple color and are in the form of an oil-soluble dye, an acid dye, a direct dye, or a basic dye. Among these, xanthene oil-soluble dyes, xanthene basic dyes, and xanthene acid dyes are preferred because they have excellent hues. These dyes may also be in the form of lake pigments obtained by making these dyes into lakes, inorganic salts of acid dyes having acidic groups such as sulfonic acid and carboxylic acid, salt-forming compounds of acid dyes and nitrogen-containing compounds, and sulfonic acid amide compounds of acid dyes.

[0064] Xanthene oil-soluble dyes include CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 42, CI Solvent Red 43, CI Solvent Red 44, CI Solvent Red 45, CI Solvent Red 46, CI Solvent Red 47, CI Solvent Red 48, CI Solvent Red 49, CI Solvent Red 50, CI Solvent Red 51, CI Solvent Red 52, CI Solvent Red 53, CI Solvent Red 54, CI Solvent Red 55, CI Solvent Red 56, CI Solvent Red 57, CI Solvent Red 58, CI Solvent Red 59, CI Solvent Red 60, CI Solvent Red 61, CI Solvent Red 62, CI Solvent Red 63, CI Solvent Red 64, CI Solvent Red 65, CI Solvent Red 66, CI Solvent Red 49, CI Solvent Red 72, CI Solvent Red 73, CI Solvent Red 109, CI Solvent Red 140, CI Solvent Red 141, CI Solvent Red 237, CI Solvent Red 246, CI Solvent Violet 2, CI Solvent Violet 10, etc. Among these, rhodamine oil-soluble dyes with high color development such as CI Solvent Red 35, CI Solvent Red 36, CI Solvent Red 49, CI Solvent Red 109, CI Solvent Red 237, CI Solvent Red 246, and CI Solvent Violet 2 are more preferred. Examples of xanthene basic dyes include CI Basic Red 1 (Rhodamine 6GCP), CI Basic Red 8 (Rhodamine G), and CI Basic Violet 10 (Rhodamine B). Among these, it is preferable to use CI Basic Red 1 and CI Basic Violet 10 because of their excellent color development properties. As xanthene acid dyes, it is preferable to use CI Acid Red 51 (Erythrosine (Food Red No. 3)), CI Acid Red 52 (Acid Rhodamine), CI Acid Red 87 (Eosine G (Food Red No. 103)), CI Acid Red 92 (Acid Phloxine PB (Food Red No. 104)), CI Acid Red 289, CI Acid Red 388, Rose Bengal B (Food Red No. 5), Acid Rhodamine G, and CI Acid Violet 9. Among these dyes, it is most preferable to use CI Acid Red 52, which is a rhodamine acid dye, in view of its excellent color development, heat resistance, and light resistance.

[0065] When used in combination with the above red pigment, yellow pigment, orange pigment, or dye, the content of the pigment containing the compound represented by the above general formulas (1) to (3) is 10 to 90 mass %, preferably 20 to 80 mass %, based on 100 mass % of the total colorant. If the content of the pigment containing the compound represented by the above general formulas (1) to (3) is 10 mass % or less, the excellent effects of brightness and coloring power cannot be fully exhibited.

[0066] <Average primary particle size of pigment> The average primary particle size of the pigment was measured (calculated) by the following method. Propylene glycol monomethyl ether acetate was added to the pigment powder, a small amount of Disperbyk-161 was added as a resin-type dispersant, and the mixture was dispersed in an ultrasonic cleaner for 1 minute to prepare a measurement sample. Three photographs (three fields of view) were taken of this sample using a transmission electron microscope (JEOL Ltd. "JEM-1200EX"), in which more than 100 primary particles of the pigment could be confirmed, and the size of 100 primary particles was measured in order from the top left of each photograph. Specifically, the minor axis diameter and major axis diameter of each primary particle of the pigment were measured in nm units, and the average was taken as the primary particle diameter of the pigment. A total of 300 distributions were created in 5 nm increments, and the median value of the 5 nm increments (for example, 8 nm for a particle diameter of 6 nm to 10 nm) was approximated as the particle diameter of the particles, and the number-average particle diameter was calculated based on the particle diameter and the number of particles.

[0067] <Fine particle size of colorant> The pigment used in the present invention can be used after being finely divided. It is also preferable to use the pigment containing the compound represented by the above general formulas (1) to (3) after being finely divided, but the method of finely dividing is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation methods can be used, and as exemplified in the present invention, a salt milling treatment using a kneader method, which is one type of wet grinding, can be used.

[0068] The primary particle size of the finely divided pigment is preferably 20 nm or more because it is easily dispersed in the colorant carrier. Also, it is preferably 100 nm or less because it is possible to form a filter segment with a high contrast ratio. The particularly preferred range is 25 to 85 nm.

[0069] Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while being heated using a kneader, a trimix, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or other kneading machine, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed during salt milling by utilizing the high hardness of the inorganic salt. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment with a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

[0070] As the water-soluble inorganic salt, sodium chloride, potassium chloride, sodium sulfate, etc. can be used, but sodium chloride (table salt) is preferably used from the viewpoint of cost. From the viewpoints of both processing efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, and most preferably 300 to 1000 parts by mass, per 100 parts by mass of the colorant.

[0071] The water-soluble organic solvent is not particularly limited as long as it functions to wet the pigment and the water-soluble inorganic salt, dissolves (mixes) in water, and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes easily evaporated, a high boiling point solvent with a boiling point of 120°C or more is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, and most preferably 50 to 500 parts by mass, per 100 parts by mass of the colorant.

[0072] When the pigment is subjected to salt milling, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. can be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the above organic solvents. The amount of the resin used is preferably in the range of 5 to 200 parts by mass relative to 100 parts by mass of the colorant.

[0073] In addition, when the pigment is subjected to salt milling, a dye derivative, which will be described later, may be added as necessary. The structure of the dye derivative used is not particularly limited, and examples thereof include compounds in which a basic substituent, an acidic substituent, or a phthalimidomethyl group that may have a substituent is introduced into an organic pigment, an anthraquinone, an acridone, or a triazine. These may be used alone or in combination of two or more kinds.

[0074] The amount of these dye derivatives used is preferably from 2 to 30 parts by mass, and most preferably from 5 to 20 parts by mass, per 100 parts by mass of the colorant.

[0075] <Coloring composition for color filters> The coloring composition for color filters of the present invention is composed of a binder resin in addition to the coloring agent described above.

[0076] <Binder resin> The binder resin disperses, dyes, or penetrates the colorant, and examples of the binder resin include thermoplastic resins. When the binder resin is used in the form of an alkali development type color resist material, it is preferable to use a binder resin having an acidic group. It is preferable to use an alkali-soluble vinyl resin copolymerized with an 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.

[0077] In particular, by using an active energy ray curable resin having an ethylenically unsaturated double bond in the side chain in an alkali development type color resist material, the resin is three-dimensionally crosslinked when a coating film is formed by exposure to active energy rays, and the colorant is fixed, improving heat resistance and suppressing fading of the colorant due to heat (deterioration of spectral characteristics). In addition, there is also an effect of suppressing aggregation and precipitation of the colorant component in the development process.

[0078] The binder resin preferably has a spectral transmittance of 80% or more, and more preferably 95% or more, over the entire wavelength range of 400 to 700 nm in the visible light region.

[0079] In order to disperse the colorant favorably, the weight average molecular weight (Mw) of the binder resin is preferably in the range of 10,000 to 100,000, and more preferably in the range of 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

[0080] When the binder resin is used as a photosensitive coloring composition for color filters, the balance between the carboxyl group acting as a colorant adsorption group and an alkali-soluble group during development, and the aliphatic and aromatic groups acting as affinity groups for the colorant carrier and solvent is important for the dispersibility, permeability, developability, and durability of the colorant, and it is preferable to use a resin with an acid value of 20 to 300 mgKOH / g. If the acid value is less than 20 mgKOH / g, the solubility in the developer is poor, making it difficult to form a fine pattern. If the acid value is more than 300 mgKOH / g, no fine pattern will remain.

[0081] The binder resin is preferably used in an amount of 20 parts by mass or more relative to 100 parts by mass of the total mass of the colorant, since it has good film-forming properties and various resistances, and is preferably used in an amount of 1,000 parts by mass or less, since it has a high colorant concentration and can express good color characteristics.

[0082] Examples of thermoplastic resins used for the binder resin include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylenes (HDPE, LDPE), polybutadiene, and polyimide resins. Of these, it is preferable to use acrylic resins.

[0083] Examples of the vinyl alkali-soluble resin copolymerized with an acidic group-containing ethylenically unsaturated monomer include resins having an acidic group such as a carboxyl group or a sulfone group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / maleic acid (anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth)acrylic acid copolymer, or an isobutylene / maleic acid (anhydride) copolymer, etc. Among these, at least one resin selected from an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer, particularly an acrylic resin having an acidic group, is preferably used because of its high heat resistance and transparency.

[0084] 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). can be done.

[0085] [Method (i)] Method (i) can be exemplified by a method in which an unsaturated ethylenic monomer having an epoxy group is copolymerized with one or more other monomers to obtain a copolymer, and a carboxyl group of an unsaturated monobasic acid having an unsaturated ethylenic double bond is subjected to an addition reaction with the side-chain epoxy group of the copolymer, and then a polybasic acid anhydride is reacted with the resulting hydroxyl group to introduce an unsaturated ethylenic double bond and a carboxyl group.

[0086] Examples of the unsaturated ethylenic monomer having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4 epoxybutyl (meth)acrylate, and 3,4 epoxycyclohexyl (meth)acrylate, which may be used alone or in combination of two or more. In terms of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)acrylate is preferred.

[0087] Examples of the unsaturated monobasic acid include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position. These may be used alone or in combination of two or more kinds.

[0088] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., which may be used alone or in combination of two or more. If necessary, such as to increase the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups. In addition, if tetrahydrophthalic anhydride or maleic anhydride having an unsaturated ethylenic double bond is used as the polybasic acid anhydride, the number of unsaturated ethylenic double bonds can be further increased.

[0089] As a method similar to the method (i), for example, there is a method in which an unsaturated ethylenic monomer having an epoxy group is added to a part of the side chain carboxyl groups of a copolymer obtained by copolymerizing an unsaturated ethylenic monomer having a carboxyl group with one or more other monomers, thereby introducing an unsaturated ethylenic double bond and a carboxyl group.

[0090] [Method (ii)] Method (ii) includes a method in which an unsaturated ethylenic monomer having a hydroxyl group is used and copolymerized with another monomer of an unsaturated monobasic acid having a carboxyl group or with another monomer, and the side chain hydroxyl group of the copolymer is reacted with an isocyanate group of an unsaturated ethylenic monomer having an isocyanate group.

[0091] Examples of the unsaturated ethylenic monomer having a hydroxyl group include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate, which may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above hydroxyalkyl (meth)acrylates, and (poly)esters obtained by addition of (poly)γ-valerolactone, (poly)ε-caprolactone, and / or (poly)12-hydroxystearic acid, etc., may also be used. Mono(meth)acrylates can also be used. From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl(meth)acrylate or glycerol(meth)acrylate is preferred.

[0092] Examples of the unsaturated ethylenic monomer having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis[(meth)acryloyloxy]ethyl isocyanate, but are not limited thereto and two or more types can be used in combination.

[0093] <Organic solvent> The coloring composition of the present invention contains an organic solvent in order to facilitate the formation of a filter segment by thoroughly dispersing and penetrating the coloring agent in the coloring agent carrier and applying the composition to a substrate such as a glass substrate so as to give a dry film thickness of 0.2 to 5 μm. The organic solvent is selected in consideration of the good applicability of the coloring composition, the solubility of each component of the coloring composition, and safety.

[0094] Examples of the organic solvent include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-ethoxyethyl propionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutanol, and the like. 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 ethyl ether, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate,Dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol 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, n-butyl acetate, isoamyl acetate, vinegar, Examples of the solvent include isobutyl acetate, propyl acetate, dibasic acid esters, etc. These solvents may be used alone or in combination of two or more kinds in any ratio as required.

[0095] The solvent can be used in an amount of 100 to 10,000 parts by mass, and preferably 500 to 5,000 parts by mass, relative to 100 parts by mass of the colorant in the colored composition.

[0096] <Photopolymerizable monomer> The photopolymerizable monomer that may be added to the colored composition of the present invention includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to form a transparent resin.

[0097] Examples of monomers and oligomers that harden when exposed to ultraviolet light or heat to produce a transparent resin include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, and the like. Examples of the photopolymerizable compounds include, but are not limited to, various acrylic acid esters and methacrylic acid esters such as ethylol ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, ester acrylate, (meth)acrylic acid ester of methylol melamine, epoxy (meth)acrylate, and urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile. These photopolymerizable compounds can be used alone or in a mixture of two or more kinds at any ratio as necessary.

[0098] The content of the photopolymerizable monomer is preferably 5 to 500 parts by mass, and more preferably 10 to 400 parts by mass, based on 100 parts by mass of the colorant, from the viewpoints of photocurability and developability.

[0099] <Photopolymerization initiator> The coloring composition of the present invention can be prepared in the form of a solvent-developable or alkali-developable photosensitive coloring composition by adding a photopolymerization initiator to cure the composition by ultraviolet irradiation and form a filter segment by a photolithography method.

[0100] Examples of photopolymerization initiators include acetophenone-based compounds such as 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-[4-(4-morpholinyl)phenyl]-1-butanone, and 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one; benzoin-based compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzoic acid, benzoylbenzoic acid methyl ... benzophenone compounds such as phenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; Triazine compounds; 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'-methoxystyryl)-6-triazine; 1,2-octanedione, 1-[4-(phenylthio)-, 2-(O-benzoyloxime ) or O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or 2,4,6-trimethylbenzoyldiphenylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. These photopolymerization initiators can be used alone or in combination of two or more at any ratio as required.

[0101] The content of the photopolymerization initiator is preferably 1 to 500 parts by mass, and more preferably 5 to 400 parts by mass, relative to 100 parts by mass of the colorant, from the viewpoints of photocurability and developability.

[0102] <Sensitizer> Furthermore, the coloring composition for color filters of the present invention may contain a sensitizer. Examples of sensitizers include unsaturated ketones such as chalcone derivatives and dibenzalacetone, 1,2-diketone derivatives such as benzil and camphorquinone, polymethine dyes such as benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, Examples of the sensitizer include squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, and Michler's ketone derivatives. These sensitizers can be used alone or in combination of two or more at any ratio as required.

[0103] Further specific examples include, but are not limited to, sensitizers described in "Dye Handbook" edited by Makoto Okawara et al. (Kodansha, 1986), "Chemistry of Functional Dyes" edited by Makoto Okawara et al. (CMC, 1981), and "Special Functional Materials" edited by Chuzo Ikemori et al. (CMC, 1986). In addition, sensitizers that exhibit absorption in the ultraviolet to near infrared range are also known. It is also possible to include a sensitizer. Among the above sensitizers, particularly suitable sensitizers include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole are used.

[0104] The content of the sensitizer is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the photopolymerization initiator contained in the colored composition, from the viewpoints of photocurability and developability.

[0105] <Multifunctional thiol> The coloring composition for color filters of the present invention may contain a polyfunctional thiol. The polyfunctional thiol is a compound having two or more thiol (SH) groups. When used together with the above-mentioned photopolymerization initiator, the polyfunctional thiol acts as a chain transfer agent in the radical polymerization process after light irradiation, and generates thiyl radicals that are not easily inhibited by oxygen, so that the resulting coloring composition for color filters has high sensitivity. In particular, polyfunctional aliphatic thiols in which the SH group is bonded to an aliphatic group such as a methylene or ethylene group are preferred.

[0106] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane ... Examples of the polyfunctional thiols include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. These polyfunctional thiols can be used alone or in combination of two or more at any ratio as required.

[0107] The content of the polyfunctional thiol is preferably from 0.05 to 100 parts by mass, and more preferably from 1.0 to 50.0 parts by mass, relative to 100 parts by mass of the colorant. By using 0.05 parts by mass or more of a polyfunctional thiol, better development resistance can be obtained. When a monofunctional thiol having one thiol (SH) group is used, such improvement in development resistance cannot be obtained.

[0108] <Leveling agent> In order to improve the leveling property of the composition on a transparent substrate, it is preferable to add a leveling agent to the coloring composition 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 Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK-Chemie Co., Ltd. Specific examples of dimethylsiloxane having a polyester structure in the main chain include BYK-310 and BYK-37 manufactured by BYK-Chemie Co., Ltd. 0. 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 1.0 part by mass with respect to 100 parts by mass of the total mass of the colored composition.

[0109] Particularly preferred leveling agents are those that have a hydrophobic group and a hydrophilic group in the molecule, have low solubility in water despite having a hydrophilic group, and have the characteristic of low surface tension reduction ability when added to a coloring composition. Furthermore, those that have good wettability to glass plates despite having low surface tension reduction ability are useful, and those that can sufficiently suppress electrostatic charge at an addition amount that does not cause defects in the coating film due to foaming are preferably used. As a leveling agent having such preferred characteristics, dimethylpolysiloxanes having polyalkylene oxide units are preferably used. Examples of polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units, and dimethylpolysiloxanes may have both polyethylene oxide units and polypropylene oxide units.

[0110] The bonding form of the polyalkylene oxide unit with the dimethylpolysiloxane may be any of a pendant type in which the polyalkylene oxide unit is bonded to the repeating unit of the dimethylpolysiloxane, a terminal modified type in which the polyalkylene oxide unit is bonded to the end of the dimethylpolysiloxane, and a linear block copolymer type in which the polyalkylene oxide unit is bonded alternately and repeatedly to the dimethylpolysiloxane. Dimethylpolysiloxane having polyalkylene oxide units is commercially available from Dow Corning Toray Co., Ltd., and examples thereof include, but are not limited to, FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207.

[0111] It is also possible to supplementarily add an anionic, cationic, nonionic, or amphoteric surfactant to the leveling agent. Two or more types of surfactants may be mixed and used. Examples of anionic surfactants supplementarily added to the leveling agent include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate, etc.

[0112] Examples of cationic surfactants to be added to the leveling agent as supplementary agents include alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of nonionic surfactants to be added to the leveling agent as supplementary agents include polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, polyethylene glycol monolaurate, etc.; alkyl betaines such as alkyl dimethylamino acetate betaine, amphoteric surfactants such as alkyl imidazolines, and fluorine-based and silicone-based surfactants.

[0113] <UV absorbers, polymerization inhibitors> The coloring composition for color filters of the present invention may contain an ultraviolet absorber or a polymerization inhibitor. By containing an ultraviolet absorber or a polymerization inhibitor, the shape and resolution of the pattern can be controlled.

[0114] Examples of the ultraviolet absorber include hydroxyphenyl triazines such as 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine; benzotriazoles such as 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol and 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole; benzophenones such as 2-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone; salicylates such as phenyl salicylate and p-tert-butylphenyl salicylate; cyanoacrylates such as ethyl-2-cyano-3,3'-diphenylacrylate; and hindered amines such as 2,2,6,6,-tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, and poly[[6-[(1,1,3,3-tetrabutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino]. These ultraviolet absorbers can be used alone or in combination of two or more in any ratio as required.

[0115] Examples of the polymerization inhibitor include hydroquinone derivatives and phenol compounds such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol, amine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine, copper and manganese salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate, nitroso compounds such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine, and ammonium salts or aluminum salts thereof. These polymerization inhibitors can be used alone or in a mixture of two or more at any ratio as necessary.

[0116] The ultraviolet absorber and polymerization inhibitor can be used in an amount of 0.01 to 20 parts by mass, and preferably 0.05 to 10 parts by mass, based on 100 parts by mass of the colorant in the colored composition. By using 0.01 parts by mass or more of an ultraviolet absorber or a polymerization inhibitor, better resolution can be obtained.

[0117] <Antioxidants> The coloring composition for color filters of the present invention can contain an antioxidant to increase the transmittance of the coating film. The antioxidant prevents the photopolymerization initiator contained in the coloring composition for color filters from being oxidized and yellowed by the heat process during heat curing or ITO annealing, and can increase the transmittance of the coating film. Therefore, by containing an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

[0118] Preferable examples of the antioxidant include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfide-based antioxidants. More preferable examples are hindered phenol-based antioxidants, hindered amine-based antioxidants, and phosphorus-based antioxidants. These antioxidants can be used alone or in combination of two or more kinds at any ratio as required.

[0119] Hindered phenol antioxidants include 2,4-bis[(laurylthio)methyl ]-o-cresol, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl), 1,3,5-tris(4-t-butyl-3-hydroxy-2,6-dimethylbenzyl), 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and the like.

[0120] Hindered amine antioxidants include bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(N-methyl-2,2,6,6-tetramethyl-4-piperidyl)sebacate, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)(1,2,3,4-butanetetracarboxylate), poly[{6-(1,1,3,3-tetramethylbutyl)imino-1,3,5-triazine-2,4-diyl}{(2,2,6,6- tetramethyl-4-piperidyl)imino}hexamethyl{(2,2,6,6-tetramethyl-4-piperidyl)imino}], poly[(6-morpholino-1,3,5-triazine-2,4-diyl){(2,2,6,6-tetramethyl-4-piperidyl)imino}hexamethine{(2,2,6,6-tetramethyl-4-piperidyl)imino}], a polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, and N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazine-2-yl]-4,7-diazadecane-1,10-diamine.

[0121] Examples of phosphorus-based antioxidants include tris[2-[[2,4,8,10-tetrakis(1,1-dimethylethyl)dibenzo[d,f][1,3,2]dioxaphosphepin-6-yl]oxy]ethyl]amine, tris[2-[(4,6,9,11-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphepin-2-yl)oxy]ethyl]amine, and ethyl bis(2,4-ditert-butyl-6-methylphenyl)phosphite.

[0122] Examples of the sulfide antioxidants include 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

[0123] The content of the antioxidant is preferably 0.1 to 5 parts by mass in 100 parts by mass of the total solid content of the coloring composition for color filters. If the content of the antioxidant is less than 0.1 parts by mass, the effect of increasing the transmittance is small, and if it is more than 5 parts by mass, the hardness is significantly reduced and the sensitivity of the coloring composition for color filters is significantly reduced.

[0124] <Other ingredients> The coloring composition for color filters of the present invention may contain an adhesion improver such as a silane coupling agent in order to improve adhesion to a transparent substrate, or an amine compound having a function of reducing dissolved oxygen.

[0125] Examples of the silane coupling agent include vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane; (meth)acrylic silanes such as γ-methacryloxypropyltrimethoxysilane; β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane; epoxy silanes such as N-β(aminoethyl)γ-aminopropyl trimethoxysilane, N-β(aminoethyl)γ-aminopropyl triethoxysilane, N-β(aminoethyl)γ-aminopropyl methyl diethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyl trimethoxysilane, N-β(aminoethyl)γ-aminopropyl methyl diethoxysilane, γ-aminopropyl triethoxysilane, γ-aminopropyl trimethoxysilane, N-phenyl-γ-aminopropyl trimethoxysilane, N-phenyl-γ-aminopropyl triethoxysilane, and thiosilanes such as γ-mercaptopropyl trimethoxysilane and γ-mercaptopropyl triethoxysilane.

[0126] The silane coupling agent can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the colorant in the coloring composition.

[0127] Examples of the amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

[0128] <Method of producing coloring composition for color filters> The coloring composition for color filters of the present invention can be produced by finely dispersing a colorant in a colorant carrier such as a resin and / or a solvent, together with a dispersion aid as necessary, using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more types of colorants may be dispersed simultaneously in a colorant carrier, or may be mixed with those dispersed separately in colorant carriers. The epoxy compound may be added at the stage of preparing the colorant dispersion, and the same effect can be obtained by adding it later to the prepared colorant dispersion. When the solubility of a colorant such as a dye is high, specifically, when the solubility in the solvent used is high, and the colorant is dissolved by stirring and no foreign matter is confirmed, it is not necessary to produce the colorant by fine dispersion as described above.

[0129] In addition, when used as a photosensitive coloring composition (resist material) for color filters, it can be prepared as a solvent-developable or alkali-developable coloring composition. The solvent-developable or alkali-developable coloring composition can be prepared by mixing the colorant dispersion, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other pigment dispersants, and additives. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

[0130] <Dispersion aid> When dispersing the colorant in the colorant carrier, not only the resin-type dispersant but also a dispersing aid such as a dye derivative, a surfactant, etc. may be appropriately contained. The dispersing aid has a large effect of preventing the colorant from re-aggregating after dispersion, so that the coloring composition obtained by dispersing the colorant in the colorant carrier using the dispersing aid has good brightness and storage stability.

[0131] <Resin-type dispersant> The coloring composition for color filters of the present invention preferably contains a resin-type dispersant. Resin-type dispersants have a colorant affinity site that has the property of adsorbing to a colorant and a site that is compatible with a colorant carrier, and act to adsorb to a colorant and stabilize the dispersion of the colorant in the colorant carrier. Specific examples of resin-type dispersants include polyurethane, polycarboxylate esters such as polyacrylate, unsaturated polyamides, polycarboxylates, polycarboxylates (partially Examples of the dispersants that can be used include oil-based dispersants such as amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylate esters, and modified products thereof, amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters, which can be used alone or in a mixture of two or more types, but are not necessarily limited to these.

[0132] Commercially available resin-type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, and 2155 manufactured by BYK Japan. or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, 6919, or Lactimon, Lactimon-WS, or Bykumen, etc., SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 2700 manufactured by Lubrizol Japan 0, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402 manufactured by BASF , 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0133] The resin-type dispersant used in the present invention is preferably one having an acidic substituent, and among them, one having an aromatic carboxyl group is preferred because it is particularly effective in preventing reagglomeration of the colorant after dispersion. As the resin-type dispersant having an aromatic carboxyl group, one containing the following (S1) or (S2) is preferred. (S1) A resin-type dispersant which is a reaction product between a hydroxyl group of a polymer having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride. (S2) A resin-type dispersant which is a polymer obtained by polymerizing an ethylenically unsaturated monomer in the presence of a reaction product between a hydroxyl group of a compound having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride.

[0134] [Resin-type dispersant (S1)] The resin-type dispersant (S1) can be produced by known methods such as those described in WO2008 / 007776, JP2008-029901A, and JP2009-155406A. The polymer (p) having a hydroxyl group is preferably a polymer having a hydroxyl group at the end, and can be obtained, for example, as a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) in the presence of a compound (q) having a hydroxyl group. The compound (q) having a hydroxyl group is preferably a compound having a hydroxyl group and a thiol group in the molecule. Since it is preferable that the terminal hydroxyl groups are plural, among them, a compound (q1) having two hydroxyl groups and one thiol group in the molecule is preferably used.

[0135] That is, a more preferred example of a polymer having two hydroxyl groups at one end can be obtained as a polymer (p1) by polymerizing an ethylenically unsaturated monomer (r) including a monomer (r1) in the presence of a compound (q1) having two hydroxyl groups and one thiol group in the molecule. The hydroxyl groups of the polymer (p) having hydroxyl groups react with the acid anhydride groups of the tricarboxylic acid anhydride and / or tetracarboxylic acid dianhydride to form ester bonds, while the anhydride ring opens to generate a carboxylic acid.

[0136] [Resin-type dispersant (S2)] The resin-type dispersant (S2) can be produced by known methods such as those described in JP 2009-155406 A, JP 2010-185934 A, and JP 2011-157416 A, and is obtained, for example, by polymerizing an ethylenically unsaturated monomer (r) in the presence of a reaction product between a hydroxyl group of a compound (q) having a hydroxyl group and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride. Among them, a polymer obtained by polymerizing an ethylenically unsaturated monomer (r) including a monomer (r1) in the presence of a reaction product between a hydroxyl group of a compound (q1) having two hydroxyl groups and one thiol group in the molecule and an acid anhydride group of a tricarboxylic acid anhydride and / or a tetracarboxylic acid dianhydride is preferred.

[0137] The difference between (S1) and (S2) is whether the polymer moiety obtained by polymerizing the ethylenically unsaturated monomer (r) is introduced first or later. The molecular weight and other properties may differ slightly depending on various conditions, but in theory, the same product can be produced if the raw materials and reaction conditions are the same.

[0138] The resin-type dispersant is preferably used in an amount of about 5 to 200 parts by mass relative to 100 parts by mass of the colorant, and from the viewpoint of film-forming properties, it is more preferably used in an amount of about 5 to 100 parts by mass.

[0139] <Dye derivatives> The coloring composition for color filters of the present invention may further contain a dye derivative. The dye derivative may be contained in an azo pigment. The dye derivative used in the present invention may be a known dye derivative having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. Examples include compounds having an acidic functional group such as a sulfo group, a carboxy group, or a phosphate group, and their amine salts, compounds having a basic functional group such as a sulfonamide group or a tertiary amino group at the terminal, and compounds having a neutral functional group such as a phenyl group or a phthalimidoalkyl group. Examples of organic dyes include diketopyrrolopyrrole pigments, phthalocyanine pigments such as copper phthalocyanine, zinc phthalocyanine, aluminum phthalocyanine, halogenated copper phthalocyanine, halogenated zinc phthalocyanine, halogenated aluminum phthalocyanine, and metal-free phthalocyanine; anthraquinone pigments such as aminoanthraquinone, diaminodianthraquinone, anthrapyrimidine, flavanthrone, anthranthrone, indanthrone, pyranthrone, and violanthrone; quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo. More specifically, JP-A-61-246261, JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-11-199796, JP-A-2001-172520, JP-A-2001-220520, JP 2002-201377 A, JP 2003-165922 A, JP 2003-168208 A, JP 2003-171594 A, JP 2004-217842 A, JP 2005-213404 A, JP 2006-291194 A, JP 2007-079094 A, JP 200 JP-A-7-226161, JP-A-2007-314681, JP-A-2007-314785, JP-A-2008-31281, JP-A-2009-57478, WO2009 / 025325 pamphlet, WO2009 / 081930 pamphlet, JP-A-2011-162662, WO2011 / 052617 pamphlet, JP-A-2012-172092 Examples of the dye derivatives include those described in JP 2012-208329 A, JP 2012-226110 A, WO2012 / 102399 A, JP 2014-5439 A, WO2016 / 163351 A, JP 2017-156397 A, and Japanese Patent No. 5753266 A, and these can be used alone or in a mixture of two or more. In these documents, the dye derivative may be described as a derivative, pigment derivative, pigment dispersant, or simply a compound, but the compound having a functional group such as an acidic group, a basic group, or a neutral group in the organic dye residue is synonymous with the dye derivative.

[0140] Among the dye derivatives used in the present invention, dye derivatives having a basic substituent are preferred because they have a significant effect of suppressing aggregation between pigments.Furthermore, organic dye residues derived from diketopyrrolopyrrole pigments, anthraquinone pigments, quinophthalone pigments, and azo pigments are preferred from the viewpoint of hue and contrast.

[0141] The dye derivative is preferably used in an amount of about 1 to 60 parts by mass, and more preferably about 5 to 30 parts by mass, based on 100 parts by mass of the colorant, from the viewpoint of color characteristics.

[0142] <Surfactant> Examples of the surfactant include anionic surfactants such as sodium lauryl sulfate, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium stearate, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, monoethanolamine of styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphate esters; nonionic surfactants such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; cationic surfactants such as alkyl quaternary ammonium salts and their ethylene oxide adducts; alkyl betaines such as alkyl dimethylaminoacetate betaine, and amphoteric surfactants such as alkyl imidazolines. These can be used alone or in combination of two or more, but are not necessarily limited to these.

[0143] When a surfactant is added, the amount is preferably 0.1 to 55 parts by mass, and more preferably 0.1 to 45 parts by mass, relative to 100 parts by mass of the colorant. If the content of the surfactant is less than 0.1 parts by mass, it is difficult to obtain the effect of adding the surfactant, and if the content is more than 55 parts by mass, the excess dispersant may affect the dispersion.

[0144] <Removal of large particles> The coloring composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation, filtration with a sintered filter or membrane filter, etc. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

[0145] <Color filters> Next, the color filter of the present invention will be described. The color filter of the present invention comprises a red filter segment, a green filter segment, and a blue filter segment on a substrate, and may further comprise a magenta filter segment, a cyan filter segment, or a yellow filter segment, and at least one of the filter segments is formed from the coloring composition of the present invention.

[0146] <Manufacturing method for color filters> The color filter of the present invention can be manufactured by a printing method or a photolithography method. The formation of filter segments by a printing method can be patterned by simply repeating printing and drying of a colored composition prepared as a printing ink, and is therefore a low-cost and mass-productive manufacturing method for color filters. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. In order to perform printing, it is preferable to use a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, control of the fluidity of the ink on the printing machine is also important, and the ink viscosity can be adjusted by using a dispersant or an extender pigment.

[0147] When the filter segment is formed by the photolithography method, the coloring composition prepared as the above-mentioned solvent-developable or alkali-developable colored resist material is applied to a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed to ultraviolet light through a mask having a predetermined pattern that is provided in contact with or not in contact with the film. Thereafter, the uncured part is removed by immersing in a solvent or an alkali developer or spraying the developer by a spray or the like to form a desired pattern, and the same operation is repeated for other colors to produce a color filter. Furthermore, heating can be performed as necessary to promote polymerization of the colored resist material. According to the photolithography method, a color filter with higher accuracy than the above-mentioned printing method can be produced.

[0148] In the development, an aqueous solution of sodium carbonate, sodium hydroxide, etc. is used as an alkaline developer, and an organic alkali such as dimethylbenzylamine, triethanolamine, etc. can also be used. In addition, a defoaming agent or a surfactant can also be added to the developer. In order to increase the sensitivity to ultraviolet light exposure, after the colored resist material is coated and dried, a water-soluble or alkaline water-soluble resin, such as polyvinyl alcohol or a water-soluble acrylic resin, may be coated and dried to form a film for preventing polymerization inhibition due to oxygen, and then ultraviolet light exposure may be performed.

[0149] The color filter of the present invention can be manufactured by the above-mentioned method, as well as by the electrodeposition method, the transfer method, the inkjet method, etc., and the coloring composition of the present invention can be used for any of these methods. The electrodeposition method is a method of manufacturing 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 of forming a filter segment in advance on the surface of a peelable transfer base sheet, and transferring the filter segment to a desired substrate.

[0150] Before forming each color filter segment on a base material such as a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film with a light-shielding agent dispersed therein can be used, but is not limited to these. Also, a thin film transistor (TFT) can be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment can be formed. Also, an overcoat film, a transparent conductive film, or the like can be formed on the color filter of the present invention as necessary.

[0151] The dry film thickness of the filter segment and black matrix is ​​preferably 0.2 to 10 μm, more preferably 0.2 to 5 μm. When drying the coating film, a reduced pressure dryer, a convection oven, an IR oven, a hot plate, or the like may be used.

[0152] The color filter is bonded to an opposing substrate using a sealant, liquid crystal is injected through an injection port provided in the seal portion, the injection port is then sealed, and a polarizing film or a retardation film is bonded to the outside of the substrate as necessary, thereby producing a liquid crystal display panel.

[0153] Such LCD panels can be used in LCD display modes that use color filters such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertically aligned (VA), and optically concentric bend (OCB).

[0154] The transparent substrate may be a glass plate such as soda-lime glass, low-alkali borosilicate glass, or non-alkali aluminoborosilicate glass, or a resin plate such as polycarbonate, polymethyl methacrylate, or polyethylene terephthalate. A transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the glass plate or resin plate for driving the liquid crystal after the panel is formed. EXAMPLES

[0155] The present invention will be described below based on examples, but the present invention is not limited thereto. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0156] <Weight average molecular weight of resin (Mw)> The weight average molecular weight (Mw) of the resin is the polystyrene-equivalent weight average molecular weight (Mw) measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, using THF as the developing solvent. <How to identify azo pigments> The azo pigment of the present invention was identified using a Bruker Daltonics MALDI mass spectrometer Autoflex III (hereinafter referred to as TOF-MS), and was identified based on the agreement between the molecular ion peak in the obtained mass spectrum and the mass number obtained by calculation.

[0157] <Contrast ratio of coating> Light emitted from a backlight unit for liquid crystal displays is polarized by passing through a polarizing plate, passes through a dried coating film of a coloring composition applied on a glass substrate, and reaches the polarizing plate. If the polarization planes of the polarizing plate and the polarizing plate are parallel, the light passes through the polarizing plate, but if the polarization planes are 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 coloring composition, scattering by pigment particles occurs, and if a part of the polarization plane is shifted, the amount of light passing through the polarizing plate decreases when the polarizing plate is parallel, and part of the light passes through the polarizing plate when the polarizing plate is perpendicular. This transmitted light was measured as the luminance on the polarizing plate, and the ratio (contrast ratio) of the luminance when the polarizing plate is parallel to the luminance when the polarizing plate is perpendicular was calculated. (Contrast ratio) = (Luminance when parallel) / (Luminance when perpendicular) The luminance meter used was a color luminance meter (Topcon Corporation's "BM-5A"), and the polarizing plate used was a polarizing plate (Nitto Denko Corporation's "NPF-G1220DUN"). During the measurement, a black mask with a 1 cm square hole was placed over the measurement area to block unnecessary light.

[0158] First, the acrylic resin solution, the resin-type dispersant solution, the colorant, the colored composition, and the method for producing the photosensitive colored composition used in the Examples, Production Examples, and Comparative Examples will be described.

[0159] <Method of manufacturing acrylic resin solution> (Preparation of acrylic resin solution 1) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 196 parts of cyclohexanone was charged in the reaction vessel, which was then heated to 80°C. The atmosphere in the reaction vessel was replaced with nitrogen, and a mixture of 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours from the dropping tube. After the dropping was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content, and methoxypropyl acetate was added to the resin solution previously synthesized so that the non-volatile content was 20% to prepare acrylic resin solution 1. The weight average molecular weight (Mw) was 26,000.

[0160] (Preparation of acrylic resin solution 2) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirrer. A reaction vessel was charged with 207 parts of cyclohexanone, the temperature was raised to 80°C, and the atmosphere inside the reaction vessel was replaced with nitrogen. Then, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110, manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis( ... A mixture of 1.33 parts of isobutyronitrile was added dropwise over 2 hours. After the dropwise addition, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and dry air was injected for 1 hour while stirring the entire amount of the obtained copolymer solution, and then the mixture was cooled to room temperature, and a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After the dropwise addition, the reaction was continued for another 1 hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the resin solution previously synthesized so that the non-volatile content was 20% to prepare an acrylic resin solution 2. The weight average molecular weight (Mw) was 18,000.

[0161] <Method of producing resin-type dispersant solution> (Preparation of resin-type dispersant solution 1) A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, and 20 parts of benzyl methacrylate, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 10 parts of 3-mercapto-1,2-propanediol was added and reacted for 10 hours. It was confirmed that 95% had reacted by measuring the solid content. 20 parts of pyromellitic anhydride, 200.0 parts of methoxypropyl acetate, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was continued at 120°C for 7 hours. It was confirmed that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and the reaction was terminated, and a polyester dispersant with an acid value of 77 mgKOH / g and a number average molecular weight of 8500 was obtained. Methoxypropyl acetate was added thereto so that the solid content was 40% by solid content measurement, thereby obtaining a resin-type dispersant solution 1 having an aromatic carboxyl group.

[0162] (Preparation of resin-type dispersant solution 2) Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, and 10 parts of benzyl methacrylate were added. 20 parts of ethyl acetate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 ° C., and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 10 parts of 3-mercapto-1,2-propanediol was added and reacted for 10 hours. It was confirmed that 95% had reacted by solid content measurement. 36 parts of trimellitic anhydride, 200.0 parts of methoxypropyl acetate, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 120 ° C. for 7 hours. It was confirmed that 98% or more of the acid anhydride was half-esterified by acid value measurement, and the reaction was terminated to obtain a polyester dispersant with an acid value of 109 mg KOH / g and a number average molecular weight of 8500. Methoxypropyl acetate was added to this so that the solid content was 40% by solid content measurement, and a resin-type dispersant solution 2 having an aromatic carboxyl group was obtained.

[0163] (Preparation of resin-type dispersant solution 3) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 6.5 parts of 3-mercapto-1,2-propanediol, 4.0 parts of pyromellitic anhydride, 0.01 parts of dimethylbenzylamine, and 41.8 parts of methoxypropyl acetate were charged, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 100°C and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70°C, and 67 parts of methyl methacrylate, 5.0 parts of methacrylic acid, 16.0 parts of t-butyl acrylate, 10.0 parts of hydroxymethyl methacrylate, and 2.0 parts of ethyl acrylate were charged, and 0.10 parts of 2,2'-azobisisobutyronitrile and 60.0 parts of methoxypropyl acetate were added, and the reaction was continued for 10 hours. The reaction was terminated after confirming that the polymerization had progressed to 95% by solid content measurement, yielding a polyester dispersant with an acid value of 43 mgKOH / g and a number average molecular weight of 15000. Methoxypropyl acetate was added to this to give a solid content of 40% by solid content measurement, yielding resin-type dispersant solution 3 having an aromatic carboxyl group.

[0164] (Preparation of resin-type dispersant solution 4) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 6.5 parts of 3-mercapto-1,2-propanediol, 4.0 parts of pyromellitic anhydride, 0.01 parts of dimethylbenzylamine, and 41.8 parts of methoxypropyl acetate were charged, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 100°C and reacted for 7 hours. After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70°C, and 67 parts of methyl methacrylate, 5.0 parts of methacrylic acid, 16.0 parts of t-butyl acrylate, 10.0 parts of (3-ethyloxetan-3-yl)methyl methacrylate, and 2.0 parts of ethyl acrylate were charged, and 0.10 parts of 2,2'-azobisisobutyronitrile and 60.0 parts of methoxypropyl acetate were added and reacted for 10 hours. The reaction was terminated after confirming that the polymerization had progressed to 95% by solid content measurement, yielding a polyester dispersant with an acid value of 47 mgKOH / g and a number average molecular weight of 15000. Methoxypropyl acetate was added to this to give a solid content of 40% by solid content measurement, yielding resin-type dispersant solution 4 having aromatic carboxyl groups.

[0165] (Preparation of Resin-Type Dispersant Solution 5) In a flask equipped with a condenser and stirrer, add AIBN (2,2'-azobisisobutyronitrile). 1.0 part by mass of dimethylaminoethyl methacrylate and 186 parts by mass of propylene glycol monomethyl ether acetate were added, followed by 27 parts by mass of methyl methacrylate, 27 parts by mass of butyl methacrylate, 21 parts by mass of 2-ethylhexyl methacrylate, 18 parts by mass of benzyl methacrylate, and 3.6 parts by mass of cumyl dithiobenzoate, and the mixture was purged with nitrogen for 30 minutes. The mixture was then gently stirred to raise the temperature of the reaction solution to 60°C, and this temperature was maintained for 24 hours to carry out living radical polymerization. Next, a solution of 1.0 part by mass of AIBN and 35 parts by mass of dimethylaminoethyl methacrylate dissolved in 70 parts by mass of propylene glycol monomethyl ether acetate and purged with nitrogen for 30 minutes was added to the reaction solution, and living radical polymerization was carried out at 60°C for 24 hours to obtain a solution of a block copolymer. The obtained block copolymer 25 parts by mass of benzyl chloride and 50 parts by mass of propylene glycol monomethyl ether were added to the copolymer solution, and the mixture was reacted at 80°C for 2 hours to adjust the solid content to 40%. Thus, a resin-type dispersant solution 5 was obtained. The resin-type dispersant 5 is a block copolymer consisting of an A block having repeating units derived from methacryloyloxyethyl benzyl dimethyl ammonium chloride and dimethylaminoethyl methacrylate, and a B block having repeating units derived from methyl methacrylate, butyl methacrylate, 2-ethylhexyl methacrylate, and benzyl methacrylate. As a result of proton NMR measurement, the copolymerization ratio of each repeating unit was methacryloyloxyethyl benzyl dimethyl ammonium chloride / dimethylaminoethyl methacrylate / methyl methacrylate / butyl methacrylate / 2-ethylhexyl methacrylate / benzyl methacrylate=34 / 4 / 18 / 18 / 14 / 12 (mass ratio).

[0166] <Method of producing dye derivative> The production method and structure of the dye derivative used in the present invention are shown below, but the present invention is not limited thereto.

[0167] (Production of dye derivative 1) 16 parts of 5-nitroisophthalic acid and 1.0 part of N,N-dimethylformamide (DMF) were dissolved in 110 parts of toluene. 22.6 parts of thionyl chloride were added dropwise over 25 minutes, and the mixture was refluxed at 110°C for 1 hour to synthesize 5-nitroisophthalic acid dichloride. 38.0 parts of 4-amino-N-(3-(diethylamino)propyl)benzamide were dispersed in 90 parts of toluene, and the above 5-nitroisophthalic acid dichloride was added dropwise at room temperature over 1 hour, and the mixture was refluxed for 4 hours to complete the reaction. After distilling off the toluene while neutralizing with a 10% aqueous sodium carbonate solution, the mixture was reslurried in a 3% aqueous NaOH solution, filtered, and dried to obtain 28.0 parts of a compound represented by the following formula 8. formula 8 [ka]

[0168] Next, 25.0 parts of the compound represented by the above formula 8 were dissolved in 100 parts of N-methylpyrrolidone, and an aqueous solution of 32 parts of sodium hydrosulfide hydrate (containing 65% sodium hydrosulfide) dissolved in 55 parts of water was added thereto, followed by refluxing for 6 hours to obtain 20.0 parts of the base compound represented by the following formula 10. formula 9 [ka]

[0169] 20.0 parts of the base compound represented by the above formula 9 was dispersed in 200 parts of water, ice was added to adjust the temperature to 5°C, 20.0 parts of 35% hydrochloric acid aqueous solution was added and stirred for 1 hour, then an aqueous solution prepared by adding 3.60 parts of sodium nitrite to 11.0 parts of water was added and stirred for 2 hours. Then, an aqueous solution consisting of 59.0 parts of 80% acetic acid aqueous solution, 65.0 parts of 25% sodium hydroxide aqueous solution, and 64.0 parts of water was added to obtain a diazonium salt aqueous solution. Meanwhile, 18.7 parts of N-[2-methoxy-5-chlorophenyl]-3-hydroxy-2-naphthalenecarboxamide and 53.5 parts of 25% sodium hydroxide aqueous solution were dissolved in 340 parts of methanol to obtain a coupler solution.

[0170] This coupler solution was poured into the above diazonium salt aqueous solution at 5°C over 30 minutes to carry out a coupling reaction. The pH at this time was 4.4. After stirring for 1 hour 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 35.8 parts of dye derivative 1 represented by formula 10.

[0171] Formula 10 [ka]

[0172] (Production of dye derivative 2) Dye derivative 2 represented by formula 11 was prepared with reference to Preparation Example 3 of Japanese Patent No. 1863188. Formula 11 [ka]

[0173] (Production of dye derivative 3) With reference to Example 1 of Japanese Patent No. 5316690, dye derivative 3 represented by formula 12 was prepared. Formula 12 [ka]

[0174] (Preparation of dye derivative 4) With reference to Synthesis Example 3 of Japanese Patent No. 5748665, dye derivative 4 represented by formula 13 was produced. Formula 13 [ka]

[0175] (Production of dye derivative 5) Dye derivative 5 represented by formula 14 was prepared with reference to Preparation Example 21 of Japanese Patent No. 4396778. formula 14 [ka]

[0176] (Production of dye derivative 6) Dye derivative 3 represented by formula 15 was prepared with reference to Preparation Example 6 of Japanese Patent No. 4983061. formula 15 [ka]

[0177] (Production of dye derivative 7) With reference to Example 12 of Japanese Patent No. 4993026, dye derivative 7 represented by formula 16 was prepared. formula 16 [ka]

[0178] <Production of azo pigments> [Example 1] (Manufacture of azo pigment 1) 181 parts of the base compound [B-1] represented by formula 17 to 1500 parts of N-methylpyrrolidone After adding, 294 parts of 35% hydrochloric acid was added and cooled to -2 to 0°C. 208 parts of 25% aqueous sodium nitrite solution was added to this solution, and the mixture was stirred for 30 minutes while maintaining the temperature at 0 to 5°C to prepare a diazonium solution. Separately, a coupler solution consisting of 167 parts of coupler compound [C-1] represented by formula 18, 316 parts of 25% sodium hydroxide solution, and 1500 parts of methanol was prepared. The prepared diazonium solution and coupler solution were simultaneously dropped into 1000 parts of acetate buffer solution at pH 5.4 over 10 minutes. The reaction formula at this time is represented by formula 19. After the dropwise addition, the mixture was stirred for 30 minutes at room temperature, and then further stirred while maintaining the temperature at 80°C, and the precipitated reaction product was filtered, washed with hot water, and dried to obtain 340 parts of azo pigment 1 represented by formula 20. As a result of mass analysis by TOF-MS, it was identified as azo pigment 1. The average primary particle diameter was 51 nm.

[0179] Base compound [B-1] formula 17 [ka]

[0180] Coupler compound [C-1] formula 18 [ka]

[0181] Reaction Equation formula 19 [ka]

[0182] Azo Pigment 1 formula 20 [ka]

[0183] [Examples 2 to 116] (Manufacture of azo pigments 2-116) Azo pigments 2 to 116 were obtained by carrying out the same operation as in the production of azo pigment 1, except that the base compound [B-1] and coupler compound [C-1] used in the production of azo pigment 1 were changed to the compounds represented by R, X, and A in Tables 1 to 3, respectively, and the amounts added were adjusted so that the molar numbers of the base compound and coupler compound were consistent with those in Example 1. The reaction formulas at this time are represented by Formulas 21 to 23. As a result of mass analysis by TOF-MS, the azo pigments were identified as 2 to 116. In Tables 1 to 3, Ph represents a phenyl group.

[0184] Reaction Equation formula 21 [ka]

[0185] [Table 1]

[0186] Reaction Equation formula 22 [ka]

[0187] [Table 2]

[0188] Reaction Equation formula 23 [ka]

[0189] [Table 3]

[0190] Formulas (3-1) to (3-3) in Table 3 are as follows.

[0191] Formula (3-1) [ka] Formula (3-2) [ka] Formula (3-3) [ka]

[0192] [Example 117] (Manufacture of azo pigment 117) 72 parts of azo pigment 1, 8 parts of dye derivative 1, 800 parts of sodium chloride, and 90 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded for 6 hours at 60° C., and subjected to salt milling treatment. The kneaded product obtained was poured into 3 liters of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, which was then filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol, and then dried at 80° C. for one day to obtain 76 parts of azo pigment 117.

[0193] [Examples 118 to 140] (Manufacture of azo pigments 118-140) Azo pigments 118 to 140 were obtained in the same manner as Azo Pigment 117, except that the azo pigment and dye derivative used in Azo Pigment 117 were replaced with the azo pigments and dye derivatives shown in Table 4 in terms of their types and ratios.

[0194] [Table 4]

[0195] <Manufacture of other colorants> [Manufacturing Examples 1-13] (Production of Red Colorant 1: PR254) 100 parts of commercially available CI Pigment Red 254 (PR254) (BASF's "Irgazin Red D3656 HD"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.), kneaded for 6 hours at 60°C, and subjected to salt milling treatment. The kneaded product obtained was added to 3 liters of warm water, heated to 70°C and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for a day and night to obtain 98 parts of red colorant 1. The average primary particle diameter was 33 nm.

[0196] (Production of Red Colorant 2: PR177) The same procedure as for the production of Red Colorant 1 was carried out, except that CI Pigment Red 254 (BASF's "Irgazin Red D3656 HD") was used instead of CI Pigment Red 177 (PR177) (Sinilex Red SR3C) manufactured by Shinic, to obtain 97 parts of Red Colorant 2. The average primary particle diameter was 37 nm.

[0197] (Production of Red Colorant 3: PR242) The same procedure as for the production of Red Colorant 1 was carried out, except that CI Pigment Red 254 (BASF's "Irgazin Red D3656 HD") was used instead of CI Pigment Red 242 (PR242) (Clariant's "Sandorin Scarlet 4RF"), to obtain 98 parts of Red Colorant 3. The average primary particle diameter was 39 nm.

[0198] (Production of Red Colorant 4: PR269) Manufacture of red colorant 1, except that CI Pigment Red 254 (BASF's "Irgazin Red D3656 HD") was changed to CI Pigment Red 269 (PR269) (Sanyo Pigment Co., Ltd.'s "Permanent Carmine 3810"). Thus, 98 parts of Red Colorant 4 was obtained. The average primary particle size was 35 nm.

[0199] (Production of Red Colorant 5: PR291) The same procedure as for the production of Red Colorant 1 was carried out except that CI Pigment Red 254 (BASF's "Irgazin Red D3656 HD") was used instead of CI Pigment Red 291 (PR291) (CINIC's "Cinilex DPP MT-CF"), to obtain 98 parts of Red Colorant 5. The average primary particle diameter was 45 nm. (Production of Red Colorant 6) The following red colorant 6 was synthesized with reference to Example 1 of Japanese Patent No. 6368844. The average primary particle size was 43 nm.

[0200] Red colorant 6 [ka]

[0201] (Production of Yellow Colorant 1: PY138) 500 parts of quinophthalone-based yellow pigment CI Pigment Yellow 138 (BASF "Paliotol Yellow L0962-HD"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 120°C. Next, this kneaded product was put into 5 liters of warm water, heated to 70°C and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for a day and night to obtain 490 parts of yellow colorant 1. The average primary particle diameter was 63 nm.

[0202] (Production of Yellow Colorant 2: PY139) 500 parts of an isoindoline-based yellow pigment, CI Pigment Yellow 139 (BASF's "Paliotol Yellow L1820"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 120°C. Next, this kneaded mixture was poured into 5 liters of warm water, heated to 70°C and stirred for 1 hour to form a slurry, which was then filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol. After removing ethylene glycol, the mixture was dried at 80° C. overnight to obtain 510 parts of Yellow Colorant 2. The average primary particle diameter was 68 nm.

[0203] (Production of Yellow Colorant 3: PY150) 500 parts of azo-based yellow pigment CI Pigment Yellow 150 (Clariant's "Hostaperm Yellow HN4G"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 120°C. Next, this kneaded mixture was put into 5 liters of warm water, heated to 70°C and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for a day and night to obtain 500 parts of yellow colorant 3. The average primary particle diameter was 60 nm.

[0204] (Preparation of Yellow Colorant 4: Quinophthalone Compound (b)) 40 parts of 8-aminoquinaldine, 150 parts of 2,3-naphthalenedicarboxylic anhydride, and 154 parts of benzoic acid were added to 200 parts of methyl benzoate, heated to 180°C, and stirred for 4 hours. After cooling to room temperature, the reaction mixture was poured into 5440 parts of acetone and stirred at room temperature for 1 hour. The product was filtered, washed with methanol, and dried to obtain 116 parts of quinophthalone compound (c). As a result of mass analysis by TOF-MS, it was identified as quinophthalone compound (c).

[0205] Quinophthalone Compounds (c) [ka]

[0206] Furthermore, using the quinophthalone compound (c) as a raw material, a compound (c-2) was obtained according to the synthesis method described in JP-A-2008-81566.

[0207] Compound (c-2) [ka]

[0208] 100 parts of compound (c-2), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, heated to 180° C., and reacted for 4 hours. The production of quinophthalone compound (b) and the disappearance of the raw material compound (c-2) were confirmed by MS. After cooling to room temperature, the reaction mixture was poured into 3510 parts of acetone and stirred at room temperature for 1 hour. The product was filtered, washed with methanol, and dried to obtain 120 parts of quinophthalone compound (b). As a result of mass analysis by TOF-MS, it was identified as quinophthalone compound (b). Quinophthalone Compound (b) [ka]

[0209] 500 parts of the quinophthalone compound (b) obtained above, 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 120° C. Next, this kneaded product was put into 5 liters of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. for 24 hours to obtain 480 parts of yellow colorant 4. The average primary particle diameter was 62 nm.

[0210] (Production of green colorant 1: PG58) 200 parts of a phthalocyanine green pigment CI Pigment Green 58 (DIC Corporation's "FASTOGEN GREEN A110"), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this kneaded mixture was added to 8000 parts of warm water, heated to 80°C and stirred for 2 hours to form a slurry, filtered and washed with water repeatedly to remove the sodium chloride and diethylene glycol, and then dried at 85°C for a day and night to obtain 190 parts of green colorant 1. The average primary particle diameter was 69 nm.

[0211] (Preparation of blue dye 1: PB15:6) 200 parts of phthalocyanine blue pigment CI Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by Toyo Color Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80° C. Next, this kneaded product was put into 8000 parts of warm water, heated to 80° C. and stirred for 2 hours to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 85° C. for a day and night to obtain 190 parts of blue colorant 1. The average primary particle diameter was 74 nm.

[0212] (Preparation of purple dye 1: PV23) 200 parts of a dioxazine-based purple pigment CI Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyo Color Co., Ltd.), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80°C for 6 hours. Next, this kneaded mixture was poured into 8000 parts of warm water and kneaded for 8 hours. The mixture was heated to 0° C. and stirred for 2 hours to form a slurry, which was then filtered and repeatedly washed with water to remove sodium chloride and diethylene glycol, and then dried overnight at 85° C. to obtain 190 parts of purple colorant 1. The average primary particle size was 69 nm.

[0213] <Method of producing colored composition> [Example 201] (Preparation of Coloring Composition (RM-1)) The mixture below was stirred and mixed until homogeneous, and then dispersed in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours. The mixture was then filtered through a filter with a pore size of 5.0 μm to produce a colored composition (RM-1) with a non-volatile content of 20% by mass. Colorant (azo pigment 1): 10.8 parts Dye derivative 1: 1.2 parts Acrylic resin solution 1: 19.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts Resin-type dispersant solution 1: 10.4 parts

[0214] [Examples 202 to 376, Comparative Examples 1 to 3] (Coloring composition (RM-2~177, RCM-2, RCM-4) The following colored compositions (RM-2 to 177, RCM-2, RCM-4) were prepared in the same manner as the colored composition (RM-1), except that the composition was changed to that shown in Table 5. When a resin-type dispersant was not used, the acrylic resin solution 1 was added instead to match the solid content. When a dye derivative was not used, a colorant was added instead to match the solid content.

[0215] <Production of other coloring compositions> (Coloring composition (RCM-1): PR254) The mixture below was stirred and mixed to be homogenous, and then dispersed for 3 hours in an Eiger mill (Eiger Japan Co., Ltd. "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a filter with a pore size of 5.0 μm to prepare a colored composition (RCM-1) with a non-volatile content of 20% by mass. Red colorant 1 (CI Pigment Red 254): 12.0 parts Acrylic resin solution 1: 19.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts Resin-type dispersant solution 1: 10.4 parts

[0216] (Coloring composition (RCM-3): PR242) The mixture below was stirred and mixed to be homogenous, and then dispersed for 3 hours in an Eiger mill (Eiger Japan Co., Ltd. "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a filter with a pore size of 5.0 μm to prepare a colored composition (RCM-3) with a non-volatile content of 20% by mass. Red colorant 3 (CI Pigment Red 242): 12.0 parts Acrylic resin solution 1: 19.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts Resin-type dispersant solution 1: 10.4 parts

[0217] (Coloring composition (RCM-5): PR291) The mixture below was stirred and mixed to be homogenous, and then dispersed for 3 hours in an Eiger mill (Eiger Japan Co., Ltd. "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a filter with a pore size of 5.0 μm to prepare a colored composition (RCM-5) with a non-volatile content of 20% by mass. Red colorant 5 (CI Pigment Red 291): 12.0 parts Acrylic resin solution 1: 19.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts Resin-type dispersant solution 1: 10.4 parts

[0218] (Coloring composition (YCM-1): PY138) The mixture below was stirred and mixed until homogeneous, and then dispersed for 3 hours in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a filter with a pore size of 5.0 μm to produce a colored composition (YCM-1) with a non-volatile content of 20% by mass. Yellow colorant 1 (CI Pigment Yellow 138): 12.0 parts Acrylic resin solution 1: 19.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts Resin-type dispersant solution 1: 10.4 parts

[0219] (Coloring composition (YCM-2): PY139) The mixture below was stirred and mixed to make it uniform, and then dispersed for 3 hours in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a filter with a pore size of 5.0 μm to produce a colored composition (YCM-2) with a non-volatile content of 20% by mass. Yellow colorant 2 (CI Pigment Yellow 139): 12.0 parts Acrylic resin solution 1: 19.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts Resin-type dispersant solution 1: 10.4 parts

[0220] (Coloring composition (YCM-3): PY150) The mixture below was stirred and mixed until homogenous, and then dispersed for 3 hours in an Eiger mill (Eiger Japan, "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a filter with a pore size of 5.0 μm to obtain a dispersion with a non-volatile content of 20% by mass. A color composition (YCM-3) was prepared. Yellow colorant 3 (CI Pigment Yellow 150): 12.0 parts Acrylic resin solution 1: 19.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts Resin-type dispersant solution 1: 10.4 parts

[0221] (Coloring composition (YCM-4): Quinophthalone compound (b)) The mixture below was stirred and mixed to make it uniform, and then dispersed for 3 hours in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a filter with a pore size of 5.0 μm to produce a colored composition (YCM-4) with a non-volatile content of 20% by mass. Yellow colorant 4 (quinophthalone compound (b)): 12.0 parts Acrylic resin solution 1: 19.2 parts Propylene glycol monomethyl ether acetate (PGMAc): 58.4 parts Resin-type dispersant solution 1: 10.4 parts

[0222] (Coloring composition (GCM-1): PG58) A green colored composition (GCM-1) having a non-volatile content of 20% by mass was obtained in the same manner as in the colored composition (YCM-1), except that the yellow colorant 1 (CI Pigment Yellow 138) was changed to the green colorant 1 (CI Pigment Green 58).

[0223] (Coloring composition (BCM-1): PB15:6) A blue colored composition (BCM-1) having a non-volatile content of 20% by mass was obtained in the same manner as in the colored composition (YCM-1), except that the yellow colorant 1 (CI Pigment Yellow 138) was replaced with the blue colorant 1 (CI Pigment Blue 15:6).

[0224] (Coloring composition (VCM-1): PV23) A purple colored composition (VCM-1) having a non-volatile content of 20% by mass was obtained in the same manner as in the colored composition (YCM-1), except that the yellow colorant 1 (CI Pigment Yellow 138) was changed to the purple colorant 1 (CI Pigment Violet 23).

[0225] (Evaluation of Coloring Composition) The heat resistance, foreign matter evaluation, and storage stability of the obtained colored composition and the coating film formed using the same were performed by the following methods. The evaluation results are shown in Table 5.

[0226] (Heat resistance evaluation) The colored composition was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater so that the dry film thickness was 2.0 μm, then dried at 70° C. for 20 minutes, heated at 230° C. for 60 minutes, and allowed to cool to produce a coated film substrate (one embodiment of a color filter). The chromaticity ([L * (1), a * (1), b * (1)]) was measured using a microspectrophotometer (Olympus Optical Co., Ltd., "OSP-SP100"). After that, as a heat resistance test, the sample was heated at 260°C for 1 hour, and the chromaticity ([L * (2), a * (2), b * (2)]) was measured and the color difference ΔEab was calculated using the following formula: *was determined and rated on the following four-point scale. ΔEab * = √((L * (2)- L * (1) 2 + (a * (2)-a * (1) 2 +( b * (2)-b * (1) 2 ) ◎:ΔEab * is less than 1.0 (very good) ○: ΔEab * is 1.0 or more and less than 2.5 (good) △: ΔEab * is 2.5 or more and less than 5.0 (poor) ×: ΔEab * is 5.0 or higher (extremely poor)

[0227] (Paint film foreign matter evaluation) The colored composition was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater so that the dry film thickness was 2.0 μm, then dried at 70°C for 20 minutes, and then heated at 230°C for 60 minutes and allowed to cool to produce a coated substrate. Evaluation was performed by observing the surface using an Olympus Systems metallurgical microscope "BX60." The magnification was 500 times, and the number of particles observable in any five visual fields in transmission was counted. Evaluation was performed using the following four-level scale. ◎: The number of foreign objects is less than 5 (very good) ○: The number of foreign objects is 5 or more and less than 10 (good) △: The number of foreign objects is 10 or more and less than 60 (defective). ×: 60 or more foreign objects (extremely poor quality)

[0228] (Storage stability test method) The viscosity of the colored composition at 25° C. was measured at 20 rpm using an E-type viscometer (TUE-20L model manufactured by Toki Sangyo Co., Ltd.). The viscosity change rate (%) (= (viscosity after storage at 40° C. for 7 days - initial viscosity) / initial viscosity) was calculated from the initial viscosity on the day of preparation of the colored composition and the viscosity measured after storage for 14 days in a thermostatic chamber at 40° C., and the storage stability was evaluated according to the following criteria. ◎: Viscosity change rate is less than 10% (very good) ○: Viscosity change rate is 10% or more and less than 20% (good) △: Viscosity change rate is 20% or more but less than 50% (poor) ×: Viscosity change rate is 50% or more (extremely poor)

[0229] [Table 5]

[0230] [Table 6]

[0231] [Table 7]

[0232] As shown in Tables 5 to 7, the coloring compositions using the colorants of the present invention showed good results in terms of heat resistance of the coating film, coating film foreign matter, and storage stability. In particular, the coloring compositions using red colorant 6 showed good results in terms of heat resistance of the coating film, coating film foreign matter, and storage stability. When compared with the color composition (Comparative Example 1), it was found that the storage stability was good even under more severe test conditions.

[0233] <Method for producing photosensitive coloring composition for color filters> [Example 401] (Photosensitive coloring composition (RR-1)) The following mixture (total 100 parts) was stirred and mixed to be homogeneous, and then filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive coloring composition (RR-1). Coloring composition (RM-1): 23.0 parts Coloring composition (RCM-1): 27.0 parts Acrylic resin solution 2: 7.5 parts Photopolymerizable monomer (Toagosei Co., Ltd. "Aronix M-402"): 2.0 parts Dipentaerythritol Hexaacrylate Photopolymerization initiator (BASF "OXE-02"): 1.5 parts Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) Cyclohexanone: 39.0 parts

[0234] [Examples 402 to 421, Comparative Examples 4 to 6] (Photosensitive coloring composition (RR-2~24)) As shown in Table 6, photosensitive coloring compositions (RR-2 to RR-24) were obtained in the same manner as in the case of the photosensitive coloring composition (RR-1), except that the types and ratios of the coloring compositions were adjusted. <Evaluation of photosensitive coloring composition for color filters> The luminance, contrast ratio, solvent resistance and dye migration of the obtained photosensitive coloring composition were evaluated by the following methods. Table 8 shows the evaluation results.

[0235] (Brightness evaluation) The obtained photosensitive coloring composition was applied onto a glass substrate, dried at 70°C for 20 minutes, and then heated at 230°C for 60 minutes to obtain a coated substrate having a chromaticity of x=0.683 and y=0.313 under light source C. The luminance (Y) of the obtained substrate was measured with a microspectrophotometer (Olympus Optical Co., Ltd. "OSP-SP200") and evaluated according to the following four-level scale. ◎: 13.5 or more (very good) ○: 13.0 or more, less than 13.5 (good) △: 12.5 or more, less than 13.0 (poor) ×: Less than 12.5 (very poor)

[0236] (Contrast ratio (CR) evaluation) The contrast ratio was measured using the same substrate as that used for measuring the luminance, and was evaluated using the following four-level scale. ◎: 8000 or more (very good) ○: 7000 or more to less than 8000 (good) △: 6000 to less than 7000 (defective) ×: Less than 6000 (very poor)

[0237] (Evaluation of Solvent Resistance) The photosensitive coloring composition for color filters was applied onto a glass substrate using a slit die coater, and then prebaked on a hot plate at 90° C. for 2 minutes to form a film having a thickness of 2.4 μm. The substrate on which the coating film was formed was then cooled to room temperature, and the coating film was then irradiated with radiation having wavelengths of 365 nm, 405 nm, and 436 nm at 1,000 J / m using a high-pressure mercury lamp through a striped photomask. 2 After alkaline development, the substrate was washed with ultrapure water and post-baked at 230°C for 20 minutes to form red stripe-shaped pixels on the substrate. * (1), a * (1), b * (1)]) was measured using a microspectrophotometer (Olympus Optical Co., Ltd., "OSP-SP100"). After that, the sample was immersed in N-methyl-2-pyrrolidone (NMP) for 15 minutes, and the chromaticity ([L * (2), a * (2), b * (2)]) and calculate the color difference ΔEab * was determined and evaluated according to the same criteria as for heat resistance.

[0238] (Evaluation of dye transferability) The photosensitive coloring composition for color filters was applied onto a glass substrate using a slit die coater, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating film with a thickness of 2.4 µm. Next, the substrate on which the coating film was formed was cooled to room temperature, and then the coating film was irradiated with radiation having wavelengths of 365 nm, 405 nm, and 436 nm at a rate of 1,000 J / m2 using a high-pressure mercury lamp through a striped photomask. 2 The substrate was exposed to light at an exposure dose of 100 nm. After alkaline development, the substrate was washed with ultrapure water and post-baked at 230°C for 20 minutes to form red stripe-shaped pixels on the substrate. The transmittance of the 520 nm light on the glass substrate 8 μm away from the red stripe-shaped pixels was then measured (T1). The acrylic resin solution 2 was then applied to the substrate using a slit die coater, and the substrate was pre-baked on a hot plate at 90°C for 2 minutes to form a coating film with a thickness of 2.5 μm. The substrate was post-baked at 230°C for 20 minutes. The transmittance of the 520 nm light on the glass substrate 8 μm away from the red stripe-shaped pixels was then measured (T2). The difference between T1 and T2 was taken as ΔT (%) and evaluated in the following three stages. It can be said that the smaller the ΔT value, the less the decrease in luminance due to color transfer to adjacent other color filter segments, and the more the migration is suppressed. ○: ΔT is less than 1.0% (good) △: ΔT is 1.0% or more and less than 3.0% (poor) ×: ΔT is 3.0% or more (extremely poor)

[0239] [Table 8]

[0240] From the results in Table 8, it is clear that the examples using the colorant of the present invention are excellent in brightness, contrast ratio, solvent resistance and migration. In particular, a remarkable effect was confirmed by using it instead of CI Pigment Red 177, CI Pigment Red 269 or Red Colorant 6, which are conventionally used as bluish pigments.

[0241] <Method for producing green and blue photosensitive coloring compositions for color filters> (Green photosensitive coloring composition 1: PG58 / PY138) A mixture of the following composition was stirred and mixed to be homogeneous, and then filtered through a filter having a pore size of 1.0 μm to prepare green photosensitive coloring composition 1. Green coloring composition (GCM-1): 32.0 parts Yellow coloring composition (YCM-1): 18.0 parts Acrylic resin solution 2: 7.5 parts Photopolymerizable monomer (Toagosei Co., Ltd. "Aronix M-402"): 2.0 parts Dipentaerythritol Hexaacrylate Photopolymerization initiator (BASF "OXE-02"): 1.5 parts Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(0-acetyloxime) Cyclohexanone: 39.0 parts

[0242] (Blue photosensitive coloring composition 1: PB15:6 / PV23) A blue-colored composition 1 was obtained in the same manner as the green-colored composition 1, except that 32.0 parts of the green-colored composition and 18.0 parts of the yellow-colored composition were replaced with 46.0 parts of the blue-colored composition and 4.0 parts of the purple-colored composition in total of 50.0 parts, and the total of 50.0 parts was replaced with 46.0 parts of the blue-colored composition and 4.0 parts of the purple-colored composition in total of 50.0 parts.

[0243] <Production and evaluation of color filters> The red photosensitive coloring composition (RR-1) was applied onto a glass substrate on which a black matrix had been formed, using a slit die coater, and then prebaked on a hot plate at 90°C for 2 minutes to form a coating film. Next, the substrate on which the coating film had been formed was cooled to room temperature, and then the coating film was irradiated with radiation having wavelengths of 365 nm, 405 nm, and 436 nm at 1,000 J / m using a high-pressure mercury lamp through a striped photomask. 2 After alkali development, the resist was washed with ultrapure water and then post-baked at 230° C. for 20 minutes to form red stripe-shaped pixels on the substrate. Next, in the same manner, a green stripe-shaped pixel was formed next to the red stripe-shaped pixel using the green photosensitive coloring composition 1. Furthermore, a blue stripe-shaped pixel adjacent to the red and green pixels was formed in the same manner using the blue photosensitive coloring composition 1. Next, a protective film was formed on the three pixels of red, green, and blue using a photocurable resin composition. In this way, a RGB three-color filter with high brightness and excellent durability was produced.

Claims

1. A colorant for color filters, comprising an azo pigment which is a compound represented by the following general formula (3), wherein the content of the azo pigment in 100% by mass of the total of the colorants is 20 to 80% by mass: General formula (3) 【Chemistry 1】 [In general formula (3), R １９ ~R ２３ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryloxy group which may have a substituent, a hydroxyl group, a cyano group, a nitro group, a carboxyl group, a sulfo group, -CONR ２４ R ２５ or -SO ２ N.R. ２６ R ２７ Represents R ２４ ~R ２７ each independently represents a hydrogen atom, an alkyl group which may have a substituent, or a phenyl group which may have a substituent. １９ , R ２１ and R ２２ are all hydrogen atoms, or R 23 , R 21 and R 20 are all hydrogen atoms.]

2. R in the above general formula (3) １９ ~R ２３ At least one of the following is -CONHY or -SO ２ 2. The colorant for color filters according to claim 1, wherein the colorant is NHY, where Y represents a phenyl group which may have a substituent.

3. A coloring composition for color filters, comprising a colorant and a binder resin, wherein the colorant is the colorant for color filters according to claim 1 or 2.

4. 4. The coloring composition for color filters according to claim 3, further comprising a resin-type dispersant having an acidic substituent.

5. 5. The coloring composition for color filters according to claim 4, wherein the resin type dispersant having an acidic substituent is a resin type dispersant having an aromatic carboxyl group.

6. 6. The coloring composition for color filters according to claim 3, further comprising a dye derivative, the dye derivative containing a dye derivative having a basic substituent.

7. The colorant further comprises at least one selected from the group consisting of C.I. Pigment Red 242, C.I. Pigment Red 254, C.I. Pigment Red 291, C.I. Pigment Yellow 138, C.I. Pigment Yellow 139, C.I. Pigment Yellow 150, and a yellow pigment represented by the following general formula (4): The coloring composition for color filters according to any one of claims 3 to 6. General formula (4) 【Chemistry 2】 [In general formula (4), Z １ ~Z １３ each independently represents a hydrogen atom, a halogen atom, an alkyl group which may have a substituent, an alkoxyl group which may have a substituent, an aryl group which may have a substituent, -SO ３ It represents H, --COOH, and monovalent to trivalent metal salts of these acidic groups, alkylammonium salts, a phthalimidomethyl group which may have a substituent, or a sulfamoyl group which may have a substituent. Z １ ~Z ４ and / or Z １０ ~Z １３ Adjacent groups may be joined together to form an aromatic ring which may have a substituent.

8. The coloring composition for color filters according to any one of claims 3 to 7, further comprising a photopolymerizable monomer.

9. A color filter comprising a filter segment formed from the coloring composition for color filters according to any one of claims 3 to 8 on a substrate.

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