Colorants for color filters for organic EL display devices, coloring compositions for color filters for organic EL display devices, films, color filters, and organic EL display devices

Abstract

The present invention provides colorants for color filters used in organic EL display devices, which are suitable for forming films with high coloring power, low reflectivity, and excellent solvent resistance during low-temperature curing. [Solution] The problem is solved by a coloring agent for a color filter for an organic EL display device, which contains CI pigment violet 32 ​​and a compound represented by the following formula, wherein the content of the compound represented by the following formula is 0.01 to 10.0% by mass relative to the total amount of CI pigment violet 32 ​​and the compound represented by the following formula. JPEG2026109060000032.jpg4848

Description

[Technical Field]

[0001] The present invention relates to a coloring agent for color filters for organic EL display devices, a coloring composition for color filters for organic EL display devices, a film, a color filter, and an organic EL display device. [Background technology]

[0002] In color filters used in solid-state image sensors and image display devices, CI pigment red 254 and CI pigment red 177 are widely used as colorants in coloring compositions for forming red pixels. In recent years, there has been a demand for even higher brightness, higher contrast, and higher heat resistance, and the use of benzimidazolone pigments has been proposed to meet these requirements (Patent Documents 1 and 2). However, while Patent Documents 1 and 2 propose the use of red benzimidazolone pigments, there is no mention of purple CI pigment violet 32.

[0003] Furthermore, Patent Document 3 proposes using a blue or violet pigment of a specific volume-average particle size to solve the problems of pattern straightness and surface roughness defects and to provide a colored photosensitive resin composition with excellent viscosity stability over time. However, Patent Document 3 does not specifically mention the use of CI pigment violet 32 ​​in a colored photosensitive resin composition.

[0004] While liquid crystal displays (LCDs) have been the dominant type of image display device, organic electroluminescent (OLED) displays are gaining popularity due to their low power consumption, lack of backlight requirements, and ability to be made into thin films and bendable. Furthermore, to achieve even thinner films, development is underway to eliminate the polarizing plates used to prevent light reflection in OLED displays and replace them by adding an anti-reflective function to color filters. Such color filters are desired to have high coloring power and low reflectivity, but Patent Documents 1-3 do not mention coloring power or reflectivity.

[0005] Furthermore, since organic light-emitting layers used in organic EL display devices generally have low heat resistance, it is preferable that the colored resin composition for forming color filters used in organic EL display devices be cured at a low temperature, for example, 130°C or less. Patent Document 4 proposes using a colored resin composition containing CI pigment violet 19 to provide a colored resin composition that is useful for manufacturing color filters suitable for organic EL display devices, has excellent low-temperature curing properties, and also has excellent red color reproducibility, but there is no mention of CI pigment violet 32.

[0006] Furthermore, Patent Document 5 proposes a manufacturing method for azo pigments that controls the residual amount of coupler components. Although it is stated that azo pigments produced by this manufacturing method can be suitably used in color filters and the like, there is no mention of issues such as reduced reflectivity specific to organic EL display devices or solvent resistance during low-temperature curing. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2012-215865 [Patent Document 2] Japanese Patent Publication No. 2013-149592 [Patent Document 3] Japanese Patent Publication No. 2023-123378 [Patent Document 4] Japanese Patent Publication No. 2021-103295 [Patent Document 5] WO2012-133612 publication [Overview of the project] [Problems that the invention aims to solve]

[0008] The present invention aims to provide a coloring agent for color filters used in organic EL display devices that is suitable for forming films with high coloring power, low reflectivity, and excellent solvent resistance during low-temperature curing. Furthermore, the present invention aims to provide a coloring composition for color filters used in organic EL display devices using the coloring agent, a film formed from the coloring composition, a color filter, and an organic EL display device. [Means for solving the problem]

[0009] As a result of diligent research, the inventors of the present invention have discovered that by including CI pigment violet 32 ​​and a specific compound, a coloring agent for color filters for organic EL display devices that is suitable for forming films with high coloring power, low reflectivity, and good solvent resistance during low-temperature curing can be obtained, leading to the present invention.

[0010] In other words, the present invention relates to a colorant for a color filter for an organic EL display device, comprising CI pigment violet 32 ​​and a compound represented by the following formula (1), wherein the content of the compound represented by the following formula (1) is 0.01 to 10.0% by mass relative to the total amount of CI pigment violet 32 ​​and the compound represented by the following formula (1).

[0011] Formula (1) [ka]

[0012] Furthermore, the present invention relates to a coloring composition for a color filter for an organic EL display device, comprising a coloring agent (A) containing the aforementioned coloring agent for a color filter for an organic EL display device, and a resin (B).

[0013] Furthermore, the present invention relates to a coloring composition for a color filter for an organic EL display device, wherein the resin (B) comprises a resin-type dispersant (B1) having an aromatic carboxyl group.

[0014] Furthermore, the present invention relates to a coloring composition for a color filter for an organic EL display device, wherein the resin (B) comprises a resin-type dispersant (B2) having a basic substituent.

[0015] Furthermore, the present invention relates to a coloring composition for a color filter for an organic EL display device, wherein the coloring agent (A) comprises a pigment derivative having a basic substituent.

[0016] Furthermore, the present invention relates to a coloring composition for a color filter for an organic EL display device, comprising a photopolymerizable compound (C) and / or a photopolymerizable initiator (D).

[0017] Furthermore, the present invention relates to a film formed from a coloring composition for a color filter for an organic EL display device.

[0018] Furthermore, the present invention relates to a color filter having the aforementioned film.

[0019] Furthermore, the present invention relates to an organic EL display device equipped with the aforementioned color filter. [Effects of the Invention]

[0020] According to the present invention, a coloring agent for color filters for organic EL display devices can be provided, which is suitable for forming films with high coloring power, low reflectivity, and excellent solvent resistance during low-temperature curing. Furthermore, a coloring composition for color filters for organic EL display devices using the coloring agent, a film formed from the coloring composition, a color filter, and an organic EL display device can be provided. [Modes for carrying out the invention]

[0021] The embodiments for carrying out the present invention will be described in detail below. However, the present invention is not limited to the embodiments described below and can be modified and implemented within the scope of solving the problem.

[0022] In this specification, unless otherwise specified, "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," "(meth)acryloyloxy," or "(meth)acrylamide" means "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," "acryloyloxy and / or methacryloyloxy," or "acrylamide and / or methacrylamide," respectively. Also, "CI" means Color Index (CI; issued by The Society of Dyers and Colourists).

[0023] <Colorants for color filters used in organic EL display devices> The coloring agent for color filters for organic EL display devices of the present invention comprises CI pigment violet 32 ​​and a compound represented by the following formula (1).

[0024] Formula (1) [ka]

[0025] In the present invention, the content of the compound represented by formula (1) is characterized by being 0.01 to 10.0% by mass relative to the total amount of CI pigment violet 32 ​​and the compound represented by formula (1). If it is less than 0.01% by mass, the effect of brightness improvement and reflectance reduction will decrease. If it is more than 10.0% by mass, the coloring power will decrease. It is presumed that by having a content of the compound represented by formula (1) within the above range, the pigments in the colorant are less likely to interact with each other, such as by agglomerating, and the particle size of the various particles in the colorant becomes finer, resulting in improved brightness and low reflectivity. Furthermore, it is presumed that by having a content within the above range, intermolecular hydrogen bonds are appropriately formed by the action of the benzimidazolon group and hydroxyl group, making it possible to provide a colored composition with good solvent resistance for films cured at low temperatures. From the viewpoint of the above reasons, the content of the compound represented by formula (1) is preferably 0.05 to 8.0% by mass, and more preferably 0.1 to 5.0% by mass, relative to the total amount of CI pigment violet 32 ​​and the compound represented by formula (1). As described above, the coloring agent for color filters for organic EL display devices of the present invention has high coloring power and is useful for improving properties specific to color filters for organic EL display devices, such as low reflectivity and solvent resistance during low-temperature curing.

[0026] <Coloring composition for color filters in organic EL display devices> The present invention provides a coloring composition for color filters for organic EL display devices, comprising a coloring agent (A) and a resin (B).

[0027] <Coloring agent (A)> The coloring composition for color filters for organic EL display devices of the present invention contains the coloring agent (A) of the present invention. In other words, the coloring composition for color filters for organic EL display devices of the present invention contains CI pigment violet 32 ​​and a compound represented by formula (1).

[0028] In the coloring composition for color filters for organic EL display devices of the present invention, the total amount of CI pigment violet 32 ​​and the compound represented by formula (1) is preferably 15 to 60% by mass, and more preferably 20 to 55% by mass, in the coloring agent (A).

[0029] (Other colorants) The coloring composition for color filters for organic EL display devices of the present invention may include, as colorant (A), other colorants other than CI pigment violet 32 ​​and the compound represented by formula (1). Other colorants can be arbitrarily selected from various conventionally known pigments, pigment derivatives, and dyes. As pigments, organic or inorganic pigments can be used individually or in mixtures of two or more. Pigments with high color development and high heat resistance, particularly those with high heat decomposition resistance, are preferred, and organic pigments are usually used. Specific examples of other colorants usable in the present invention are shown below by color index numbers.

[0030] [Pigments] Examples of red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 6 3:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 2 Red pigments such as 63, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, or 296, the pigment described in Japanese Patent Publication No. 2014-134712, the pigment described in Japanese Patent Publication No. 6368844, etc. can be used. In particular, from the viewpoint of brightness and coloring power, it is preferable to include at least one selected from the group consisting of C.I. Pigment Red 177, C.I. Pigment Red 179, C.I. Pigment Red 264, C.I. Pigment Red 269, and C.I. Pigment Red 122, and it is more preferable to include at least one of C.I. Pigment Red 177 and C.I. Pigment Red 264.

[0031] When the coloring composition for color filters for organic EL display devices of the present invention is a red coloring composition, the amount of red pigment is preferably 30 to 70% by mass, and more preferably 35 to 65% by mass, in the coloring agent (A).

[0032] As the orange pigment, you can use orange pigments such as CI Pigment Orange 34, 36, 38, 43, 51, 55, 59, 61, 62, 64, 71, or 73.

[0033] As for yellow pigments, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 20, 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, 86, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 125, 126, 127, Yellow pigments such as 128, 129, 137, 138, 139, 147, 148, 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, 231, 233, or 234 can be used. Yellow dyes such as quinoline-based, azo-based, disazo-based, and methine-based dyes can also be used. In particular, isoindoline pigments are preferred in terms of brightness and coloring power, CI Pigment Yellow 139 and 185 are more preferred, and CI Pigment Yellow 139 is even more preferred.

[0034] As green pigments, for example, zinc phthalocyanine pigments described in CI Pigment Green 7, 10, 36, 37, 58, 59, 62, 63, Japanese Patent Publication No. 2008-19383, Japanese Patent Publication No. 2007-320986, Japanese Patent Publication No. 2004-70342, International Publication No. 2015 / 118720, etc., and aluminum talocyanine pigments described in Japanese Patent No. 4893859, etc. can be used.

[0035] As blue pigments, for example, CI Pigment Blue 1, 1:2, 1:3, 2, 2:1, 2:2, 3, 8, 9, 10, 10:1, 11, 12, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 18, 19, 22, 24, 24:1, 53, 56, 56:1, 57, 58, 59, 60, 61, 62, 64, etc., can be used.

[0036] As purple pigments, for example, CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 37, 39, 42, 44, 47, 49, and 50 can be used.

[0037] In addition, inorganic pigments such as titanium dioxide, barium sulfate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black can be used. Inorganic pigments are used in combination with organic pigments to ensure good coating properties, sensitivity, and developability while maintaining a balance between saturation and brightness.

[0038] [Pigment derivatives] In the present invention, the colorant (A) may contain a pigment derivative. Examples of pigment derivatives include compounds having an acidic group, a basic group, a neutral group, etc., in addition to the pigment structure or triazine structure. The acidic group, basic group, neutral group, etc., may be directly bonded to the pigment structure or triazine structure, or they may be bonded via a linking group.

[0039] Examples of pigment structures include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiaidine indigo pigments, benzimidazolon pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, surene pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0040] Examples of acidic groups include sulfo groups, carboxyl groups, and phosphate groups. Examples of basic groups include sulfonamide groups and tertiary amino groups. Examples of neutral groups include salts of the above-mentioned acidic groups, salts of basic groups, phenyl groups, and phthalimide groups.

[0041] In the present invention, the pigment derivative is preferably a compound having an organic pigment structure or a triazine structure, with at least one selected from the group consisting of an acidic group, a basic group, a group having a salt structure, and a phthalimide group, and more preferably has a basic substituent.

[0042] Specific examples of pigment derivatives are shown below, but the invention is not limited to these.

[0043] <<Diketopyrrolopyrrole-based pigment derivatives>> [ka]

[0044] <<Phthalocyanine-based pigment derivatives>> [ka]

[0045] <<Anthraquinone-based pigment derivatives>> [ka]

[0046] <<Quinacridone-based pigment derivatives>>

change

[0047] <<Surface pigment derivative>>

change

[0048] <<チアジンインジゴ pigment derivative>>

change

[0049] <<Torika pigment derivatives>>

change

[0050] <<Polychrome pigment derivatives>>

change

[0051] <<Koron pigment derivative>>

change

[0052] <<Nano-based pigment derivatives>>

change

[0053] <<アゾ-based pigment inducer>>

change

[0054] In general formulas (101) to (112), (114) to (128), and (130) to (133), R 101 ~R 117 、R 129 、R 130 、R 141 ~R 145 each independently represents a hydrogen atom, a hydroxyl group, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a phthalimidomethyl group which may have a substituent, an acyl group which may have a substituent, an amino group, a sulfo group, a carboxyl group, a phosphate group, a halogen group, a group represented by general formulas (150) to (155), (158), or (159). m and n each independently represent a positive integer. However, when a molecule has a plurality of substituents, one or more of them are substituents other than a hydrogen atom. Also, when there is only one substituent in a molecule, it is a substituent other than a hydrogen atom.

[0055] In general formula (113), R 118 represents a hydrogen atom, a halogen atom, a nitro group, a cyano group, a hydroxyl group, an alkoxy group, an aryloxy group, -SO2R 177 、or -NR 178 R 179 However, R 177 represents a hydrogen atom, an alkyl group which may have a substituent, a phenyl group which may have a substituent, or a halogen atom, and R 178 and R 179 each independently represent a hydrogen atom, an alkyl group having 1 to 12 carbon atoms, or a heterocyclic ring which may contain additional nitrogen, oxygen or sulfur atoms formed integrally by R 178 and R 179 . R 119 represents a hydrogen atom, an alkyl group which may have a substituent, or an acyl group which may have a substituent. R 120 、R 121 、R 123 ~R 128Each of these independently comprises a hydrogen atom, an optionally substituted alkyl group, an optionally substituted phenyl group, a halogen atom, a cyano group, an optionally substituted alkoxy group, or NR 180 R 181 However, R 180 and R 181 These are, independently of each other, a hydrogen atom, an alkyl group which may have substituents, or R 180 and R 181 Together, they represent a heterocycle that may contain further nitrogen, oxygen, or sulfur atoms. R 122 This represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted acyl group, or a group represented by general formulas (150) to (155).

[0056] In general formula (129), R 131 ~R 140 Each of these independently represents a hydrogen atom, a halogen atom, an alkyl group, a perfluoroalkyl group, an alkoxyl group, or a group represented by general formula (150), (153), or (159). 131 ~R 140 The adjacent groups may be bonded by -NHCONH- groups to form a benzimidazolon ring. 131 ~R 140 At least one of these is a group represented by general formula (150), (153), or (159).

[0057] [ka] JPEG2026109060000018.jpg139170

[0058] In general formulas (150) to (155), X1 represents a direct bond, -SO2-, -CO-, -CH2-, -CH2NHCOCH2-, -CONHC6H4CO-, or -CONHC6H4-. Y1 is directly coupled, -NR 170 SO2-, -SO2NR 170 -, -CONR 170-, - NR 170 CO- or -CH2NR 170 COCH2NR 170 - represents Y2 represents a direct bond, an optionally substituted arylene group, or an optionally substituted heteroaromatic ring, and these groups are -NR 170 They may be linked to each other by divalent linking groups selected from -, -O-, -SO2-, or CO-. Y3 is directly bonded, -NR 170 - or -O- represents. 'o' represents an integer between 0 and 20. M1 represents hydrogen, copper, zinc, manganese, nickel, cobalt, and iron atoms. M2 represents a hydrogen atom, calcium atom, barium atom, strontium atom, manganese atom, or aluminum atom. i represents the valence of M2. R 150 and R 151 Each of these can independently be an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R 150 and R 151 Together, they represent a heterocycle that may have substituents, further containing nitrogen, oxygen, or sulfur atoms. R 152 ~R 156 , R 159 ~R 162 Each of these independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or a polyoxyalkylene group. R 157 and R 158 These are, independently, groups represented by the following general formulas (156) or (157), -O-(CH2) o -R 171 , -OR 172 , -NR 173 R 174 , represents -Cl, -F or Y3-Y2-Y1-Q, R 157 and R 158Either one of them is a group represented by the following general formula (156) or (157), -O-(CH2) o -R 171 , -OR 172 , or NR 173 R 174 That is the case. R 170 This represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group. R 171 R represents a heterocyclic residue which may have substituents. 172 ~R 174 Each of the following independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkenyl group, or an optionally substituted phenyl group, and Q represents an organic dye residue.

[0059] [ka]

[0060] In the general formula (156), Z1 is -NR 170 - represents -CONH- or -O-, and Z2 represents an optionally substituted alkylene group, an optionally substituted alkenylene group, or an optionally substituted arylene group, and these groups are -NR 170 They may be linked together by divalent linking groups selected from -, -O-, -SO2-, or CO-. However, R 170 This is R in general formulas (150) to (155). 170 It is synonymous with [the above]. R 150 and R 151 Each of these can independently be an optionally substituted alkyl group, an optionally substituted alkenyl group, an optionally substituted phenyl group, or R 150 and R 151 Together, they represent a heterocycle that may have substituents, further containing nitrogen, oxygen, or sulfur atoms.

[0061] [ka]

[0062] In general formula (157), Z3 represents a single bond connecting the triazine ring and a nitrogen atom, -NR 175 -, -NR 175 -Z4-CO-, -NR 175 -Z4-CONR 176 -, -NR 175 -Z4-SO2-, -NR 175 -Z4-SO2NR 176 -, -O-Z4-CO-, -O-Z4-CONR 175 -, -O-Z4-SO2-, or O-Z4-SO2NR 175 -, R 175 and R 176 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, or a phenyl group which may have a substituent, and Z4 represents an alkylene group which may have a substituent, an alkenylene group which may have a substituent, or an arylene group which may have a substituent. R 152 ~R 156 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, a phenyl group which may have a substituent, or a polyoxyalkylene group.

[0063]

Chemical formula

[0064]

Chemical formula

[0065] In general formula (159), X2 represents -SO2-, -CO-, -NH-, -SO2NH-, -NHSO2-, -CONH-, or -NHCO-, and R 163 ~R 167 each independently represent a hydrogen atom, an alkoxyl group, an amino group, a sulfo group, a carboxy group, a phosphoric acid group, or a group represented by general formulas (150) to (155).

[0066] The alkyl group, which may have substituents, is preferably a linear alkyl group having 1 to 20 carbon atoms, and the substituents are preferably hydrogen or halogen groups. The phthalimide alkyl group, which may have substituents, is preferably an alkyl group having 1 to 3 carbon atoms, and the substituents are preferably hydrogen or a halogen group. The acyl group, which may have substituents, is preferably an acyl group having 1 to 10 carbon atoms as an alkyl group, and preferably a hydrogen or halogen group as an substituent. The alkoxy group, which may have substituents, is preferably a linear alkoxy group having 1 to 5 carbon atoms as the alkyl group, and hydrogen or halogen groups are preferred as the substituents. The alkenyl or alkenylene group, which may have substituents, preferably has hydrogen or a linear alkyl group having 1 to 10 carbon atoms as substituents. The phenyl group, which may have substituents, preferably has hydrogen, a halogen group, a linear alkyl group having 1 to 10 carbon atoms, or an alkoxy group as substituents. The arylene group, which may have substituents, preferably has hydrogen, a halogen group, a linear alkyl group having 1 to 10 carbon atoms, or an alkoxy group as substituents. The heterocycles that may have substituents are preferably azacyclobutane, pyrrolidine, piperidine, tetrahydrofuran, tetrahydropyran, tetrahydrothiophene, and tetrahydrothiopyran, and the substituents that may be present are preferably hydrogen, halogen groups, linear alkyl groups having 1 to 10 carbon atoms, and alkoxy groups. The heteroaromatic ring, which may have substituents, is preferably pyrrole, pyridine, furan, or thiophene, and the substituents that may be present are preferably hydrogen, a halogen group, a linear alkyl group having 1 to 10 carbon atoms, or an alkoxy group.

[0067] In the coloring composition for color filters for organic EL display devices of the present invention, the pigment derivative is preferably in a total amount of 1 to 50% by mass, and more preferably in a total amount of 3 to 30% by mass, in the coloring agent (A).

[0068] [Pigment miniaturization] When using an organic pigment as a coloring agent (A), it is preferable to mix it with other raw materials after micronization. Examples of micronization methods include wet grinding, dry grinding, and dissolution extraction. Among these, salt milling by the kneader method, which is a type of wet grinding, is preferred. The average primary particle size of the organic pigment after micronization is preferably 10 to 60 nm, and more preferably 15 to 45 nm. Having the average primary particle size within the above range results in lower reflectivity and improved brightness. The average primary particle size is the average value of approximately 200 particles arbitrarily selected from magnified images of a TEM (transmission electron microscope). If the particle has a long axis and a short axis, the length of the long axis is used.

[0069] Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while heated using batch or continuous kneading machines such as kneaders, two-roll mills, three-roll mills, ball mills, attritors, sand mills, and planetary mixers, and then washed with water to remove the water-soluble inorganic salt and water-soluble organic solvent. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain pigments with a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

[0070] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. Among these, sodium chloride (table salt) is preferred from the standpoint of cost. The amount of water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, and more preferably 300 to 1000 parts by mass, per 100 parts by mass of pigment, considering both processing efficiency and production efficiency.

[0071] The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound that dissolves (miscible) in water but substantially does not dissolve the water-soluble inorganic salt. The water-soluble organic solvent is preferably a high-boiling point solvent with a boiling point of 120°C or higher, as it does not easily volatilize due to the temperature rise during salt milling. Examples of water-soluble organic solvents include 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, and liquid polypropylene glycol. The amount of water-soluble organic solvent used is preferably 5 to 1000 parts by mass, and more preferably 50 to 500 parts by mass, per 100 parts by mass of pigment.

[0072] During the salt milling process, a resin may be added as needed. Examples of resins include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in water-soluble organic solvents. The amount of resin used is preferably 5 to 200 parts by mass per 100 parts by mass of pigment.

[0073] [dye] Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Also included are derivatives of dyes and lake pigments, which are dyes that have been transformed into lakes.

[0074] Furthermore, examples of dyes include acidic dyes having acidic groups such as sulfonic acid and carboxylic acid; in the case of direct dyes, inorganic salts of acidic dyes; salt-forming compounds of acidic dyes with quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds; and salt-forming compounds such as acidic dyes with resin components having amino groups. Salt-forming compounds of acidic dyes with compounds having an onium base are also preferred due to their excellent fastness. In addition, the compounds having an onium base are preferably resins having cationic groups in their side chains.

[0075] Basic dyes include salt-forming compounds made from organic acids, perchloric acid, or metal salts thereof. Among salt-forming compounds, salt-forming compounds of basic dyes are preferred because they have excellent resistance to various substances and compatibility with pigments.

[0076] The chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), and quinoneimine dyes (oxazine dyes). Examples include dyes such as thiazine dyes, azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and rhodamine dyes. Among these, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred from the viewpoint of color characteristics such as hue, color separation, and color unevenness, with xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, and phthalocyanine dyes being more preferred. The specific structures of the dyes are described in "New Edition Dye Handbook" (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), and "Pigment Handbook" (edited by Okawara et al.; Kodansha, 1986), among others.

[0077] <Resin (B)> The colored composition for color filters in organic EL display devices according to the present invention contains resin (B). Resin (B) is incorporated for the purpose of dispersing particles such as pigments in the composition or as a binder. Resins used primarily for dispersing particles such as pigments are also called resin-type dispersants. However, such uses of the resin are just examples, and it can also be used for purposes other than those described above.

[0078] (A resin-type dispersant having aromatic carboxyl groups (B1)) The coloring composition for color filters for organic EL display devices of the present invention preferably contains a resin-type dispersant (B1) having aromatic carboxyl groups as the resin (B). The resin-type dispersant (B1) having aromatic carboxyl groups is particularly effective in preventing the re-aggregation of the coloring agent.

[0079] In a resin-type dispersant (B1) having an aromatic carboxyl group, the aromatic carboxyl group may be included in the main chain of the repeating unit or in the side chain of the repeating unit. From the viewpoint of more significantly exhibiting the effects of the present invention, it is preferable that the aromatic carboxyl group is included in the main chain of the repeating unit. In this specification, an aromatic carboxyl group is a group having a structure in which one or more carboxyl groups are bonded to an aromatic ring. In an aromatic carboxyl group, the number of carboxyl groups bonded to the aromatic ring is preferably 1 to 4, and more preferably 1 to 2.

[0080] As a resin-type dispersant (B1) having aromatic carboxyl groups in the main chain of repeating units, for example, it can be manufactured by known methods such as those described in WO2008 / 007776, JP 2008-029901, JP 2009-155406, JP 2010-185934, JP 2011-157416, JP 2009-251481, JP 2007-23195, and JP 1996-143651.

[0081] A particularly preferred example of a resin-type dispersant (B1) having aromatic carboxyl groups in the repeating main chain is one having a main chain containing an aromatic carboxylic acid ester moiety having an ester bond obtained by esterifying an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain containing a vinyl polymer moiety. The ratio of acid anhydride groups to 1 mole of hydroxyl groups is 0.9 to 1.5 moles, preferably 1.0 to 1.3 moles. Furthermore, the main chain containing the aromatic carboxylic acid ester moiety may have a structure having a encapsulation site derived from a monoalcohol, as described later. That is, the acid anhydride group remaining in the main chain is ring-opened with a monoalcohol, resulting in the presence of an alcohol ester group and a carboxyl group. By using such resins, the filterability of the colored composition is improved, foreign matter on the coating film formed by applying the colored composition is suppressed, and furthermore, the resolubility of solidified material derived from the colored composition formed in the coating apparatus in propylene glycol monomethyl ether acetate is improved during the application of the colored composition. In this specification, side chains based on vinyl polymer moieties are formed by polymerization of ethylenically unsaturated monomers. The total monomer units constituting the vinyl polymer moiety refer to the substructures derived from each ethylenically unsaturated monomer after vinyl polymerization.

[0082] [Aromatic compounds having two or more acid anhydride groups] Aromatic compounds having two or more acid anhydride groups include, for example, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, and 2,3,6,7-naphthalene Tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic acid dianhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether Examples include dianhydride, bis(triphenylphthalic acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic acid dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic acid dianhydride.

[0083] [Compounds having two or more hydroxyl groups] As described above, compounds having two or more hydroxyl groups are preferably compounds having a hydroxyl group and a thiol group in the molecule, and more preferably compounds having two hydroxyl groups and one thiol group in the molecule.

[0084] Examples of compounds having two hydroxyl groups and one thiol group in their molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0085] [Monoalcohol] Monoalcohols include, for example, methanol, ethanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, lauryl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexanol, benzyl alcohol, methylcyclohexanol, and other monoalcohols. Monoalcohols having an ether group, such as 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, etc. Examples include monoalcohols having a carbonyl group, such as methyl lactate, ethyl lactate, and diacetone alcohol. These can be used individually or in combination of two or more.

[0086] The monoalcohol is preferably a compound having an ether group or a carbonyl group. The resin can have an ether group or a carbonyl group at the end of the main chain, improving the resolubility of the resin in propylene glycol monomethyl ether acetate. Among these, 3-methoxybutanol, propylene glycol monomethyl ether, and diacetone alcohol are preferred.

[0087] The main chain, which is an aromatic carboxylic acid ester moiety, may have encapsulation sites derived from monoalcohols, as well as encapsulation sites formed by reaction with water.

[0088] Regarding the synthesis of the encapsulation site, the amount of monoalcohol used relative to the acid anhydride group is preferably 1 to 30 molar equivalents, and more preferably 1.5 to 20 molar equivalents, per equivalent of acid anhydride group remaining in the main chain. If the amount is 1 molar equivalent or more, no acid anhydride group remains, resulting in good storage stability. If the amount is 30 molar equivalents or less, transesterification reactions due to ester bonding between the monoalcohol and the dispersant are less likely to occur, and a decrease in molecular weight is less likely to occur.

[0089] [Side chains, which are vinyl polymer parts] The side chains of the resin-type dispersant (B1), which has aromatic carboxyl groups in the main chain of repeating units, are obtained by polymerizing a vinyl polymerizable compound in the presence of a compound having thiol groups. When a compound having two hydroxyl groups and one thiol group in its molecule is used as the compound having the thiol group, the main chain is formed after the side chain is formed. Furthermore, if the compound having the thiol group is the main chain after the esterification reaction (which has multiple thiol groups derived from a compound having two hydroxyl groups and one thiol group in its molecule), then side chains are formed after the main chain is formed.

[0090] (Resin-type dispersant having a basic substituent (B2)) Furthermore, the coloring composition for color filters for organic EL display devices of the present invention preferably contains a resin-type dispersant (B2) having a basic substituent as the resin (B). The resin-type dispersant (B2) having a basic substituent is preferably a resin containing repeating units having a basic group in its side chain, more preferably a copolymer having repeating units having a basic group in its side chain and repeating units not having a basic group, and even more preferably a block copolymer having repeating units having a basic group in its side chain and repeating units not having a basic group. The amine value of the resin-type dispersant (B2) having a basic group is preferably 5 to 300 mg KOH / g. The lower limit is preferably 10 mg KOH / g or more, and more preferably 20 mg KOH / g or more. The upper limit is preferably 200 mg KOH / g or less, and more preferably 100 mg KOH / g or less.

[0091] As the resin-type dispersant (B2) having a basic substituent, nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers, and urethane polymers having functional groups in their side chains such as tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocycles are preferred.

[0092] (Other resins) The coloring composition for color filters for organic EL display devices of the present invention may contain resins other than the above-mentioned resin-type dispersant having an aromatic carboxyl group (B1) and resin-type dispersant having a basic substituent (B2) (hereinafter also referred to as "other resins").

[0093] The weight-average molecular weight (Mw) of the other resins is preferably between 3,000 and 2,000,000. The upper limit is preferably 1,000,000 or less, and more preferably 500,000 or less. The lower limit is preferably 4,000 or more, and more preferably 5,000 or more.

[0094] Other resins include (meth)acrylic resin, (meth)acrylamide resin, epoxy resin, ene-thiol resin, polycarbonate resin, polyether resin, polyarylate resin, polysulfone resin, polyethersulfone resin, polyphenylene resin, polyarylene etherphosphine oxide resin, polyimide resin, polyamide-imide resin, polyolefin resin, cyclic olefin resin, polyester resin, styrene resin, and siloxane resin.

[0095] As other resins, it is also preferable to use resins having acidic groups other than aromatic carboxyl groups. Examples of acidic groups include carboxyl groups, phosphate groups, sulfo groups, and phenolic hydroxyl groups. Resins having acidic groups can also be used as alkali-soluble resins or dispersants. The acid value of the resin having acidic groups is preferably 30 to 500 mg KOH / g. The lower limit is more preferably 50 mg KOH / g or more, and even more preferably 70 mg KOH / g or more. The upper limit is more preferably 400 mg KOH / g or less, even more preferably 200 mg KOH / g or less, particularly preferably 150 mg KOH / g or less, and most preferably 120 mg KOH / g or less.

[0096] The resin (B) content in the total solid content of the coloring composition for color filters for organic EL display devices of the present invention is preferably 0.1 to 70% by mass. The lower limit is preferably 0.5% by mass or more, more preferably 1% by mass or more, even more preferably 5% by mass or more, even more preferably 10% by mass or more, and even more preferably 15% by mass or more. The upper limit is preferably less than 50% by mass, more preferably 45% by mass or less, even more preferably 40% by mass or less, even more preferably 35% by mass or less, even more preferably 30% by mass or less, and particularly preferably 25% by mass or less.

[0097] The content of the resin-type dispersant (B1) having aromatic carboxyl groups in the total solid content of the coloring composition for color filters for organic EL display devices of the present invention is preferably 5 to 40% by mass. The upper limit is preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.

[0098] Furthermore, the content of the resin-type dispersant (B1) having aromatic carboxyl groups in the resin (B) contained in the coloring composition for color filters for organic EL display devices is preferably 50 to 100% by mass. The upper limit is preferably 100% by mass or less, and more preferably 95% by mass or less. The lower limit is preferably 60% by mass or more, and more preferably 70% by mass or more.

[0099] The content of the resin-type dispersant (B2) having a basic group in the total solid content of the coloring composition for color filters for organic EL display devices of the present invention is preferably 5 to 40% by mass. The upper limit is preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.

[0100] Furthermore, the content of the resin-type dispersant (B2) having a basic group in the resin (B) contained in the coloring composition for color filters for organic EL display devices is preferably 50 to 100% by mass. The upper limit is preferably 100% by mass or less, and more preferably 95% by mass or less. The lower limit is preferably 60% by mass or more, and more preferably 70% by mass or more.

[0101] In the present invention, a resin-type dispersant having an aromatic carboxyl group (B1) and a resin-type dispersant having a basic group (B2) may be used in combination. When used in combination, the total content of the resin-type dispersant having an aromatic carboxyl group (B1) and the resin-type dispersant having a basic group (B2) in the total solid content of the colored composition for color filters is preferably 5 to 40% by mass. The upper limit is preferably 35% by mass or less, more preferably 30% by mass or less, and even more preferably 25% by mass or less. The lower limit is preferably 10% by mass or more, and more preferably 15% by mass or more.

[0102] Furthermore, when used in combination, the total content of the resin-type dispersant (B1) having aromatic carboxyl groups and the resin-type dispersant (B2) having basic groups in the resin (B) contained in the coloring composition for organic EL display devices is preferably 50 to 100% by mass. The upper limit is preferably 100% by mass or less, and more preferably 95% by mass or less. The lower limit is preferably 60% by mass or more, and more preferably 70% by mass or more.

[0103] <Photopolymerizable compound (C)> The coloring composition for color filters for organic EL display devices of the present invention can be made into a photosensitive coloring composition by including a photopolymerizable compound (C) and / or a photopolymerization initiator (D). The photopolymerizable compound (C) includes monomers or oligomers that harden upon exposure to ultraviolet light or the like to produce a transparent resin.

[0104] Photopolymerizable compound (C) is, for example, 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, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanurate EO-modified di(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate. Examples include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, various acrylic acid esters and methacrylic acid esters such as (meth)acrylic acid esters of methylolated melamine, epoxy(meth)acrylate, 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.

[0105] (Photopolymerizable compound containing an acid group) The photopolymerizable compound (C) may contain a photopolymerizable compound having an acidic group. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups.

[0106] Examples of photopolymerizable compounds having acidic groups include esters of polyhydric alcohols and (meth)acrylic acid poly(meth)acrylates containing free hydroxyl groups with dicarboxylic acids; and esters of polyhydric acids with monohydroxyalkyl (meth)acrylates. Specific examples include monoesterified compounds containing free carboxyl groups between monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and oligoesterified compounds containing free carboxyl groups between tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarbaryl acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid and monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0107] (Photopolymerizable compound containing urethane bonds) The photopolymerizable compound (C) may contain a photopolymerizable compound having a urethane bond. Examples of the photopolymerizable compound include a polyfunctional urethane acrylate obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, and a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting that with a (meth)acrylate having a hydroxyl group.

[0108] Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylates.

[0109] Furthermore, polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanates.

[0110] Photopolymerizable compound (C) can be used alone or in combination of two or more types.

[0111] The amount of photopolymerizable compound (C) is preferably 1 to 50% by mass, and more preferably 2 to 40 parts by mass, based on 100% by mass of the nonvolatile content of the colored composition. Adding an appropriate amount further improves curability and developability.

[0112] <Photopolymerizable initiator (D)> The photopolymerization initiator (D) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4 Acetophenone compounds such as -methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t Benzophenone compounds such as butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 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( Triazine compounds such as trichloromethyl-(4'-methoxystyryl)-6-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Examples include oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyl oxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-,1-(O-acetyl oxime); phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. Among these, oxime ester compounds are preferred.

[0113] Photopolymerization initiator (D) can be used alone or in combination of two or more types.

[0114] In the present invention, it is preferable that the photopolymerization initiator (D) contains an oxime ester-based photopolymerization initiator.

[0115] (Oxime ester-based photopolymerization initiator) Oxime ester-based photopolymerization initiators undergo cleavage of the NO bond in the oxime upon absorption of ultraviolet light, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly reactive radicals, resulting in improved photocurability by allowing pattern formation with less exposure compared to using other photopolymerization initiators.

[0116] Examples of oxime ester-based photopolymerization initiators include the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. 2006-342166, the compounds described in JCSPerkin II (1979, pp. 1653-1660), the compounds described in JCSPerkin II (1979, pp. 156-162), and the Journal of Photopolymer Science and Compounds described in Technology (1995, pp. 202-232), compounds described in JP 2000-66385, compounds described in JP 2000-80068, compounds described in JP 2004-534797, compounds described in JP 2006-342166, compounds described in JP 2017-19766, compounds described in Japanese Patent No. 6065596, International Publication WO2015 / 152153 Examples include compounds described in the publication, compounds described in International Publication WO2017 / 051680, compounds described in Japanese Patent Publication No. 2007-210991, compounds described in Japanese Patent Publication No. 2009-179619, compounds described in Japanese Patent Publication No. 2010-037223, compounds described in Japanese Patent Publication No. 2010-215575, compounds described in Japanese Patent Publication No. 2011-020998, and compounds described in International Publication WO2021 / 175855.

[0117] Examples of oxime ester-based photopolymerization initiators include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one. Commercially available oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (all manufactured by BASF Japan), TR-PBG-304, TR-PBG-305, TR-PBG-3057, TR-PBG-345, TR-PBG-358 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), Adeka Optomer N-1919, Adeka Arclus NCI-730, NCI-831, NCI-930 (manufactured by ADEKA Corporation). Furthermore, it is preferable to use oxime ester-based photopolymerization initiators that are colorless or highly transparent and do not easily discolor other components.

[0118] Specifically, when classified by the skeleton contained in the compound, examples include carbazole skeletons, fluorene skeletons, diphenyl skeletons, and dioxime systems having two oxime ester groups. Furthermore, as for specific structures contained in the compound, those having a hydroxyl group, a nitro group, a carbonyl group, a fluorinated carbon group, or a benzofuran are preferably used.

[0119] [Oxime ester-based photopolymerization initiator with a diphenyl skeleton] [ka]

[0120] [Oxime ester-based photopolymerization initiator with a carbazole skeleton] [ka]

[0121] [Oxime ester-based photopolymerization initiators with a fluorene skeleton] [ka]

[0122] [Oxime ester-based photopolymerizable initiator having two oxime ester groups] Examples of oxime ester-based photopolymerizable initiators include those having two oxime ester groups on either side of a carbazole skeleton or a phenothiazine skeleton, as shown below. [ka]

[0123] Among these, oxime ester-based photopolymerization initiators having a carbazole structure, oxime ester-based photopolymerization initiators having a diphenyl skeleton, and oxime ester-based photopolymerization initiators having two oxime ester groups (including those having a carbazole skeleton) are preferred, with oxime ester-based photopolymerization initiators having a carbazole structure being the most preferred.

[0124] The content of the photopolymerization initiator (D) is preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 10 parts by mass, per 100 parts by mass of the nonvolatile content of the colored composition. When an appropriate amount is added, the photocurability and developer resistance are improved and the surface condition is improved.

[0125] <Sensitizer> Furthermore, the coloring composition for color filters for organic EL display devices of the present invention may contain a sensitizer. Examples of sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiaidine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyradinoporphyrazine derivatives. Examples include phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospilopyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acylphosphine oxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0126] Among the sensitizers mentioned above, thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives are particularly suitable for sensitizing. 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, 3,6-dibenzoyl-N-ethylcarbazole, etc., can be used.

[0127] More specifically, examples of sensitizers include, but are not limited to, those described in "Pigment Handbook" (1986, Kodansha) edited by Shin Okawara et al., "Chemistry of Functional Pigments" (1981, CMC) edited by Shin Okawara et al., and "Special Functional Materials" (1986, CMC). In addition, sensitizers that exhibit absorption in the ultraviolet to near-infrared region can also be included.

[0128] Sensitizers can be used alone or in combination of two or more types.

[0129] The sensitizer content is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the photopolymerization initiator (D). Including an appropriate amount further improves curability and developability.

[0130] <Thiol-based chain transfer agents> The coloring composition for color filters in organic EL display devices of the present invention preferably contains a thiol-based chain transfer agent. By using thiols together with a photopolymerizable initiator (D), thiyl radicals are generated in the radical polymerization process after light irradiation that act as chain transfer agents and are less susceptible to polymerization inhibition by oxygen, resulting in a highly sensitive coloring composition.

[0131] Furthermore, polyfunctional aliphatic thiols with two or more thiol groups bonded to aliphatic groups such as methylene or ethylene groups are preferred. More preferably, polyfunctional aliphatic thiols with four or more thiol groups are preferred. Increasing the number of functional groups improves the polymerization initiation function, allowing curing from the surface of the pattern to near the substrate.

[0132] 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, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, and pen Examples include tetraerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferably, examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0133] Thiol-based chain transfer agents can be used alone or in combination of two or more types.

[0134] The content of thiol-based chain transfer agents is preferably 0.1 to 10% by mass, and more preferably 0.1 to 3% by mass, based on 100% by mass of the non-volatile content of the colored composition. When an appropriate amount is included, the light sensitivity and tapered shape are improved, and wrinkles are less likely to occur on the surface of the coating.

[0135] <Polymerization inhibitors> The coloring composition for color filters in organic EL display devices of the present invention may contain a polymerization inhibitor. This suppresses photosensitivity due to diffracted light on the mask during exposure in photolithography, making it easier to obtain patterns of the desired shape.

[0136] Examples of polymerization inhibitors include alkylcatechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n- Examples include alkylresorcinol compounds such as butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tripenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphine and trisnonylphenylphosphine; pyrogallol and phloroglucin.

[0137] The polymerization inhibitor content is preferably 0.01 to 0.4 parts by mass per 100% by mass of the non-volatile content of the colored composition. Within this range, the effect of the polymerization inhibitor is enhanced, resulting in improved linearity of the taper, reduced wrinkles in the coating film, and better pattern resolution.

[0138] <UV absorber> The coloring composition for color filters for organic EL display devices of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, and salicylate compounds.

[0139] The UV absorber content is preferably 5 to 70% by mass of the total 100% by mass of the photopolymerization initiator (D) and UV absorber. Including an appropriate amount further improves resolution after development.

[0140] Furthermore, the total content of the photopolymerization initiator (D) and the ultraviolet absorber is preferably 1 to 20% by mass of the non-volatile content of the colored composition. Including an appropriate amount further improves the adhesion between the substrate and the coating, resulting in good resolution.

[0141] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, and 2-[2-hydroxy-3,5-bis(α, α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, a mixture of 3-(2H-benzotriazole2-yl)-(1,1-dimethylethyl)-4-hydroxy,C7-9 side chain and linear alkyl ester, 2-(2H-benzotriazole2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl Reaction product of 3-(3-(2H-benzotriazole2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazole2-yl)-6-t-butyl Examples include 4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate.

[0142] Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction between 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester. Examples of the resulting compounds include 2,4-bis"2-hydroxy-4-butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. Other oligomeric and polymer-type compounds having a triazine structure can also be used.

[0143] Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Other oligomeric and polymeric compounds having a benzophenone structure can also be used.

[0144] Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Other oligomer and polymer type compounds having a salicylic acid ester structure can also be used.

[0145] <Antioxidant> The coloring composition for color filters in organic EL display devices of the present invention may contain an antioxidant. The antioxidant prevents the photopolymerization initiator (D) and thermosetting compounds contained in the coloring composition from oxidizing and yellowing due to the thermal process during thermosetting and ITO annealing, thereby improving the transmittance of the coating film. In particular, when the coloring agent concentration of the coloring composition is high, the amount of coating film crosslinking components decreases, so measures such as using highly sensitive crosslinking components or increasing the amount of photopolymerization initiator (D) are taken, which can lead to a phenomenon where yellowing during the thermal process becomes stronger. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

[0146] Examples of antioxidants include hindered phenol, hindered amine, phosphorus, sulfur, and hydroxylamine compounds. In this specification, antioxidants that do not contain halogen atoms are preferred.

[0147] Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred from the viewpoint of achieving both the transmittance and sensitivity of the coating film.

[0148] Antioxidants can be used alone or in combination of two or more types.

[0149] Furthermore, an antioxidant content of 0.5 to 5.0% by mass per 100% by mass of the solid content of the colored composition is more preferable because it results in good transmittance, spectral characteristics, and sensitivity.

[0150] <Leveling agent> In the coloring composition for color filters for organic EL display devices of the present invention, it is preferable to add a leveling agent in order to improve the coatability of the composition on a transparent substrate and the drying properties of the colored film. Various surfactants such as silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used as the leveling agent.

[0151] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0152] More specifically, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345 / 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 from BIC Chemie, and FZ-7002, 2110 from Toray Dow Corning Co., Ltd. Examples include 2122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

[0153] Examples of fluorine-based surfactants include surfactants or leveling agents having fluorocarbon chains.

[0154] More specifically, examples include Surflon S-242, S-243, S-420, S-611, S-651, S-386 from AGC Seimi Chemical Co., Ltd., Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS-21 from DIC Corporation, FC-4430, FC-4432 from Sumitomo 3M Limited, EF-PP31N09, EF-PP33G1, EF-PP32C1 from Mitsubishi Materials Electronic Chemicals Co., Ltd., and Futergent 602A from Neos Co., Ltd.

[0155] Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristelle ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tripenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. Examples include sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkylimidazoline, etc.

[0156] More specifically, Kao Corporation's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, L S-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L1 06, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amito 102, 105, Examples include 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic® L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA Corporation, and (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0157] Cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

[0158] More specifically, examples include Acetamine 24, Cotamin 24P, 60W, and 86P Concentrate manufactured by Kao Corporation.

[0159] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate esters.

[0160] More specifically, examples include Neos Co., Ltd.'s Futergent 100 and 150, and ADEKA Corporation's Adeka Hope YES-25, Adeka Call TS-230E, PS-440E, EC-8600, etc.

[0161] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

[0162] More specifically, examples include Anchitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0163] When the coloring composition for color filters for organic EL display devices of the present invention contains a surfactant, the amount of surfactant added is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total solid content of the coloring composition. Within this range, a good balance is achieved between the coatability, pattern adhesion, and transmittance of the coloring composition. The coloring composition for color filters for organic EL display devices of the present invention may contain only one type of surfactant or two or more types. If two or more types are included, it is preferable that their total amount be within the above range.

[0164] <Storage stabilizer> The coloring composition for color filters for organic EL display devices of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of storage stabilizers include benzyl trimethyl chloride, quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butyl pyrocatechol, tetraethylphosphine, and tetraphenylphosphine, and phosphates. The storage stabilizer can be used in an amount of 0.1 to 10% by mass, based on the total amount of coloring agent (A) (100% by mass).

[0165] <Adhesion enhancer> The coloring composition for color filters in organic EL display devices of the present invention may contain adhesion-enhancing agents such as silane coupling agents to improve adhesion to the substrate. Improved adhesion due to the adhesion-enhancing agent results in better reproduction of fine lines and improved resolution.

[0166] Adhesion enhancers include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, and N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3- Examples of silane coupling agents include aminosilanes such as aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride salts of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatetopropyltriethoxysilane. The adhesion enhancer can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the coloring agent (A) in the coloring composition. This range is preferable because it provides a greater effect and a good balance of adhesion, resolution, and sensitivity.

[0167] <Solvent> The coloring composition for color filters in organic EL display devices of the present invention may contain a solvent to facilitate the formation of a colored film by coating it onto a substrate such as glass to a dry film thickness of 0.2 to 5 μm. The solvent is selected considering good coatability of the coloring composition, solubility of each component of the coloring composition, and safety.

[0168] As the solvent, solvents commonly used in the field can be used, and their properties such as boiling point, SP value, evaporation rate, and viscosity are taken into consideration, and they are used individually or in mixtures as appropriate according to the application conditions (speed, drying conditions, etc.).

[0169] Examples of solvents that can be used include ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing both -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule but not -O-, -CO-, and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0170] Of the above solvents, it is preferable to include an organic solvent whose boiling point at 1 atm is 120°C or higher and 180°C or lower, from the viewpoint of applicability and drying properties. Among these, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferred.

[0171] <Method for manufacturing a colored composition for color filters used in organic EL display devices> The coloring composition for color filters for organic EL display devices of the present invention can be manufactured by finely dispersing a coloring agent (A) in a coloring agent carrier such as a resin (B) and / or a solvent, preferably together with a dispersion aid (pigment derivative or surfactant), using various dispersion methods 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 (coloring agent dispersion). At this time, two or more coloring agents may be dispersed simultaneously in the coloring agent carrier, or they may be dispersed separately in the coloring agent carrier and then mixed. If the coloring agent has high solubility, such as a dye, specifically if it has high solubility in the solvent used, dissolves upon stirring, and no foreign matter is detected, then it is not necessary to manufacture it by fine dispersion as described above.

[0172] Furthermore, when used as a photosensitive colored composition (resist material) for color filters, it can be prepared as a solvent-developable or alkali-developable colored composition. The solvent-developable or alkali-developable colored composition can be prepared by mixing the colorant dispersion with a photopolymerizable compound (C) and / or a photopolymerization initiator (D), and optionally a solvent, other dispersion aids, and additives. The photopolymerization initiator (D) may be added during the preparation of the colored composition, or it may be added later to the prepared colored composition.

[0173] <Removal of coarse particles> The coloring composition for color filters for organic EL display devices of the present invention is preferably subjected to the removal of coarse particles of 5 μm or larger, preferably 1 μm or larger, and more preferably 0.5 μm or larger, and any mixed dust by means of centrifugal separation at a gravitational acceleration of 3000 to 25000 G, sintered filters, or membrane filters. Thus, it is preferable that the coloring composition substantially does not contain particles of 0.5 μm or larger. More preferably, it is preferable that the particles are 0.3 μm or smaller.

[0174] <Moisture content in coloring compositions for color filters used in organic EL display devices> The coloring composition for color filters for organic EL display devices of the present invention preferably contains 2% by mass or less of water. When the water content is within the above range, excellent dispersion stability and sensitivity are maintained even after storage over time.

[0175] The water content in the coloring composition is preferably 1.8% by mass or less, and more preferably 1.6% by mass or less. If the water content is sufficiently low within this range, problems with dispersion stability and sensitivity are unlikely to occur even after storage over time.

[0176] There are no particular restrictions on the method for controlling the water content, and known methods can be used. For example, methods include manufacturing the colored composition while blowing in a dry inert gas, or adding molecular sieves after manufacturing to dehydrate it. Among these, the method of manufacturing while blowing in a dry inert gas is preferred.

[0177] The water content can be measured by known methods such as the Karl Fischer method.

[0178] <Toluene content in coloring compositions for color filters used in organic EL display devices> The coloring composition for color filters for organic EL display devices of the present invention may contain toluene, and if so, the toluene content is preferably 0.1 to 10 ppm by mass. The upper limit of the toluene content is preferably 9 ppm by mass or less, more preferably 8 ppm by mass or less, and even more preferably 7 ppm by mass or less. The lower limit is preferably 0.2 ppm by mass or more, more preferably 0.3 ppm by mass or more, and even more preferably 0.4 ppm by mass or more.

[0179] <Membrane> The film of the present invention is formed using the coloring composition for color filters for organic EL display devices of the present invention. The film may be used in a laminated state on a substrate, or the film may be peeled off from the substrate. The film may be a flat film or a film with a pattern, but a film with a pattern is preferred.

[0180] (Method for manufacturing a film) The method for manufacturing the film is not particularly limited, and known methods can be used. For example, it can be manufactured through a process of coating the colorant composition for a color filter for an organic EL display device of the present invention on a substrate.

[0181] Examples of the substrate include a substrate made of a material such as glass, resin, or silicon. An organic light-emitting layer may be formed on these substrates. Further, an imaging element such as a CCD or CMOS may be formed on the substrate. Also, a primer layer may be provided on the substrate as needed for improving adhesion to an upper layer, preventing diffusion of substances, and planarizing the substrate surface.

[0182] Known coating methods can be used. For example, the dropwise method, slit coating method, spray method, roll coating method, spin coating method, casting coating method, inkjet method, flexographic printing, screen printing, gravure printing, offset printing, etc. can be mentioned.

[0183] The thickness of the film can be appropriately adjusted according to the purpose. The thickness of the film is preferably 0.05 to 20.0 μm, and more preferably 0.3 to 10.0 μm.

[0184] Next, a pattern is formed. Examples of the method for forming a pattern include the photolithography method and the dry etching method. When using it as a flat film, the process of forming a pattern does not need to be performed, and after coating, it is dried as needed.

[0185] Hereinafter, the method for forming a pattern will be described in detail.

[0186] [When forming a pattern by the photolithography method] When forming a pattern by a photolithography method, after drying (pre-baking) as necessary the layer formed by coating the colored composition for color filters for an organic EL display device of the present invention on a substrate, it is exposed in a pattern through a mask (exposure step), and after removing the unexposed portion by alkali development (development step), the pattern is heat-treated as necessary (post-baking step).

[0187] 〔Exposure step〕 In the exposure step, the layer formed by coating is exposed to a specific pattern through a mask using an exposure device such as a stepper. As a result, the exposed portion can be cured. Examples of the active energy ray used for exposure include ultraviolet rays such as g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm). Also, light with a wavelength of 300 nm or less can be used. Examples of light with a wavelength of 300 nm or less include KrF line (wavelength 248 nm), ArF (wavelength 193 nm), and the like. Also, at the time of exposure, light may be continuously irradiated for exposure, or exposure may be performed by repeating light irradiation and pause in a short time cycle (for example, at the millisecond level or less) (pulse exposure).

[0188] 〔Development step〕 Next, by performing an alkali development treatment, the layer of the unexposed portion is eluted in an aqueous alkali solution, and only the cured portion remains to obtain a patterned film. Examples of the alkali developer include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, 1,8-diazabicyclo-[5.4.0]-7-undecene, and the like. The concentration of the alkali developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkali developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, roughening and peeling of the pattern are suppressed, and the residual film rate after development is improved. Development methods include, for example, the dip method, spray method, and paddle method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

[0189] [Post-baking process] After development, heat treatment (post-baking) can be performed as needed. Post-baking improves the durability of the film. Because the organic light-emitting layer used in organic EL display devices generally has low heat resistance, the temperature is preferably 150°C or lower, and more preferably 130°C or lower. Furthermore, the exposure time is preferably between 2 minutes and 1 hour.

[0190] [When forming a pattern using the dry etching method] When forming a pattern by dry etching, for example, a layer formed by coating a substrate with the coloring composition for organic EL display devices of the present invention is heated and cured. Next, a patterned photoresist layer is formed on the cured film, and then dry etching is performed on the cured film using an etching gas, with the patterned photoresist layer as a mask. For pattern formation by dry etching, the method described in Japanese Patent Application Publication No. 2013-064993 can be referenced.

[0191] <Color Filter> Next, the color filter of the present invention will be described. The color filter of the present invention has a film formed using the coloring composition for color filters for organic EL display devices of the present invention. The color filter of the present invention comprises a red filter segment, a green filter segment, and a blue filter segment, and may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment. It is preferable that the film formed using the coloring composition for color filters for organic EL display devices of the present invention is a color filter used in the red filter segment.

[0192] <Organic EL display device> The organic EL display device of the present invention is not particularly limited as long as it includes the color filter of the present invention and has an organic EL element as a light source. An organic EL element that emits white light containing the components of the three primary colors may be combined with the color filter, or organic EL elements that emit light in each of the RGB colors may be assigned to each pixel, and color correction may be performed by the color filter. Alternatively, the polarizing plate in the organic EL display device may be eliminated, and the color filter may be given the role of preventing light reflection. An organic EL element and quantum dots may be combined as a light source. For example, conventionally known configurations such as those described in Japanese Patent Publication No. 2018-159749, Japanese Patent Publication No. 2021-113996, WO2021 / 171870, and Japanese Patent Publication No. 2020-034913 can be used. [Examples]

[0193] The present invention will be described in more detail below with reference to examples. The materials, amounts used, proportions, processing content, and processing procedures shown in the examples can be modified as appropriate, as long as they do not depart from the spirit of the present invention. Therefore, the scope of the present invention is not limited to the specific examples shown below. In the examples, "parts" and "%" refer to "parts by mass" and "mass%", respectively.

[0194] Prior to the examples, each measurement method will be described.

[0195] The methods for measuring the weight-average molecular weight (Mw), number-average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of resin (B) are as follows.

[0196] (Average molecular weight of resins containing acidic groups) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of resins containing acid groups were measured by gel permeation chromatography (GPC) equipped with an RI detector. An HLC-8220GPC (manufactured by Tosoh Corporation) was used as the instrument, with two separation columns connected in series and two TSK-GEL SUPER HZM-N packing materials connected in series for both columns. The measurements were performed at an oven temperature of 40°C, using THF solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent and injected in 20 microliters. All molecular weights are polystyrene equivalents.

[0197] (Average molecular weight of resins containing basic groups) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of resins containing basic groups were measured using an HLC-8320GPC instrument (manufactured by Tosoh Corporation), a SUPER-AW3000 column, and a 30 mM triethylamine and 10 mM LiBr N,N-dimethylformamide solution as the eluent. All molecular weights are polystyrene equivalents.

[0198] (Acid value of resin) 0.5 to 1 g of resin solution was mixed with 80 ml of acetone and 10 ml of water and stirred to dissolve uniformly. A 0.1 mol / L aqueous KOH solution was used as the titrant, and the solution was titrated using an automatic titrator ("COM-555," manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mg KOH / g). The acid value per unit solid content of the resin was then calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

[0199] (Amine value of resin) The amine value of the resin is calculated by converting the total amine value (mgKOH / g), which was measured according to the ASTM D 2074 method, into a solid content equivalent.

[0200] <Manufacturing of resin (B)> (Aromatic carboxyl group-containing resin-type dispersant (B1-1)) In a reaction vessel equipped with a gas inlet tube, temperature control, condenser, and stirrer, 10 parts methacrylic acid, 90 parts methyl methacrylate, 50 parts ethyl acrylate, 50 parts tert-butyl acrylate, and 50 parts propylene glycol monomethyl ether acetate were charged, and the mixture was purged with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 °C, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90 °C, and a solution prepared by adding 0.2 part of 2,2'-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate was added while reacting for 7 hours. It was confirmed by solid content measurement that 95% had reacted. 19 parts of pyromellitic dianhydride, 50 parts of propylene glycol monomethyl ether acetate, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100 °C for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. Propylene glycol monomethyl ether acetate was added for dilution so that the solid content became 50% by solid content measurement, and a resin-type dispersant (B1-1) solution having an acid value of 70.5 mgKOH / g and a weight-average molecular weight of 8,500 and having an aromatic carboxyl group was obtained.

[0201] (Resin-type dispersant (B1-2) having an aromatic carboxyl group) A reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer was charged with 140 parts of methyl methacrylate, 40 parts of tert-butyl methacrylate, 20 parts of cyclohexyl acrylate, and 50 parts of propylene glycol monomethyl ether acetate, and purged with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 °C, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90 °C, and a solution prepared by adding 0.2 part of 2,2'-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate was added while reacting for 7 hours. It was confirmed by solid content measurement that 95% had reacted. Nineteen parts of pyromellitic dianhydride, fifty parts of propylene glycol monomethyl ether acetate, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and the mixture was reacted at 100°C for 7 hours. After confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value, the reaction was terminated. Propylene glycol monomethyl ether acetate was added to dilute the mixture to a solid content of 50% by measuring the solid content, yielding a resin-type dispersant (B1-2) solution with an acid value of 42.3 mg KOH / g and a weight-average molecular weight of 8700, containing aromatic carboxyl groups.

[0202] (Resin-type dispersants having aromatic carboxyl groups (B1-3)) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 7 parts of 3-mercapto-1,2-propanediol, 10 parts of pyromellitic dianhydride, 0.06 parts of N,N-dimethylbenzylamine as a catalyst, and 69 parts of propylene glycol monomethyl ether acetate were charged. After purging with nitrogen gas, the reaction was carried out at 120°C for 5 hours. Acid value measurement confirmed that more than 95% of the acid anhydride had undergone half-esterification. Next, 6 parts methacrylic acid, 24 parts methyl methacrylate, 18 parts tert-butyl methacrylate, 33 parts 2-methoxyethyl acrylate, 19 parts 2-hydroxyethyl methacrylate, and 48 parts propylene glycol monomethyl ether acetate were charged. The reaction vessel was heated to 80°C, 0.2 parts 2,2'-azobisisobutyronitrile were added, and the mixture was reacted for 10 hours. Non-volatile content measurement confirmed that more than 95% had reacted. Next, 20.4 parts of 2-isocyanatoethyl methacrylate, 0.2 parts of hydroquinone as a polymerization inhibitor, 0.03 parts of dioctyltin dilaurate as a catalyst, and 40 parts of propylene glycol monomethyl ether acetate were charged. The mixture was heated to 70°C while blowing in nitrogen gas and air, and IR measurement showed a value of 2270 cm⁻¹ based on the isocyanate group. -1The reaction was carried out until the peak disappeared. After confirming the disappearance of the peak, propylene glycol monomethyl ether acetate was added to adjust the non-volatile content to 40%, and a resin-type dispersant (B1-3) solution having aromatic carboxyl groups with an acid value of 65.7 mg KOH / g and a weight-average molecular weight of 10,000 was obtained.

[0203] (Resin-type dispersant having a basic substituent (B2-1)) In a reactor equipped with a gas inlet pipe, condenser, stirring blades, and thermometer, 40 parts methyl methacrylate, 10 parts n-butyl methacrylate, and 13.2 parts tetramethylethylenediamine as a catalyst were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, purging the system with nitrogen. Next, 9.3 parts ethyl bromoisobutyrate as an initiator, 5.6 parts cuprous chloride as a catalyst, and 133 parts methoxypropyl acetate were charged, and the temperature was raised to 110°C under a nitrogen atmosphere to start polymerization of the first block (block B). After 4 hours of polymerization, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or higher, calculated from the non-volatile content. Next, 61 parts methoxypropyl acetate, 25 parts dimethylaminoethyl methacrylate and 25 parts methacryloyloxyethyltrimethylammonium chloride as monomers for the second block (block A) were added to this reactor, and the reaction was continued while stirring was maintained at 110°C and a nitrogen atmosphere. Two hours after adding dimethylaminoethyl methacrylate, the polymerization solution was sampled and its solid content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate of the second block (block A) was 98% or higher. The reaction solution was then cooled to room temperature to stop the polymerization. GPC measurement revealed that the polymer had a Mw of 16000, a molecular weight distribution Mw / Mn of 1.4, and a reaction conversion rate of 98.5%. In this way, a resin (B2) with an amine value of 69.7 mg KOH / g per solid content was obtained. After cooling to room temperature, approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the non-volatile content was 50% by mass to prepare a resin-type dispersant (B2-1) solution with a basic substituent.

[0204] (Resin-type dispersant with basic substituents (B2-2)) A resin-type dispersant (B2-2) solution with a basic substituent was prepared by adding propylene glycol monomethyl ether acetate to BYK's DISPERBYK-2013 so that the non-volatile content was 50% by mass.

[0205] (Resin-type dispersants having basic substituents (B2-3)) A resin-type dispersant (B2-3) solution with a basic substituent was prepared by adding propylene glycol monomethyl ether acetate to BYK's DISPERBYK-2150 so that the non-volatile content was 50% by mass.

[0206] (Resin (B3)) 370 parts of cyclohexanone were placed in a separable four-necked flask equipped with a thermometer, condenser, nitrogen gas inlet tube, dropping tube, and stirrer. The temperature was raised to 80°C, and the flask was purged with nitrogen. A mixture of 30 parts dicyclopentanyl methacrylate, 10 parts styrene, 31.2 parts glycidyl methacrylate, and 2.0 parts 2,2'-azobisisobutyronitrile was then added dropwise over 2 hours via the dropping tube. After the dropwise addition, the mixture was reacted at 100°C for 3 hours. Then, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was continued at 100°C for another hour. Next, the container was replaced with an air-purging system, and 9.3 parts of acrylic acid (100% of the glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 parts of hydroquinone were added to the container. The reaction was continued at 120°C for 6 hours until the solids acid value reached 0.5, at which point the reaction was terminated to obtain a resin solution. Subsequently, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and the mixture was reacted at 120°C for 3.5 hours to obtain a resin solution. After cooling to room temperature, approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was then added to the previously synthesized resin solution to prepare resin (B3) solution so that the non-volatile content was 50% by mass. The weight-average molecular weight (Mw) was 19000.

[0207] (Resin (B4)) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer into a separable four-neck flask. 196 parts of cyclohexanone were charged into this vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 25.1 parts benzyl methacrylate, 23.0 parts n-butyl methacrylate, 14.3 parts 2-hydroxyethyl methacrylate, 13.4 parts methacrylic acid, 24.1 parts paracumylphenol ethylene oxide-modified acrylate (Toagosei Co., Ltd. "Aronics M110"), and 1.1 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the addition was complete, the reaction was continued for another 3 hours to obtain a resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was then added to the previously synthesized resin solution to achieve a non-volatile content of 50% by mass to prepare resin (B4) solution. Resin (B4) had an acid value of 87 mgKOH / g, a weight-average molecular weight of 25,000, and a composition ratio (mol%) of benzyl methacrylate / methacrylic acid / n-butyl methacrylate / 2-hydroxyethyl methacrylate / paracumylphenol ethylene oxide modified acrylate = 22 / 24 / 25 / 17 / 12.

[0208] <Manufacturing of colorants for color filters used in organic EL display devices> [Example 1] Referring to Example 81 of Publication No. WO2012-133612, a colorant V32-1 for color filters of organic EL display devices was prepared, comprising CI pigment violet 32 ​​and a compound represented by formula (1).

[0209] [Example 2] The colorant V32-1 produced in Example 1 was dispersed in 100 parts and 1000 parts methanol and stirred for 2 hours. After filtration and washing with water, the resulting wet cake was dried overnight at 80°C to produce colorant V32-2 for color filters for organic EL display devices.

[0210] [Example 3] In Example 1, 150 parts of the colorant V32-1, 1500 parts of sodium chloride, and 230 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50°C for 6 hours. Next, this mixture was added to 6000 parts of hot water and stirred for 2 hours while heating to 80°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, the mixture was dried at 80°C overnight to produce colorant V32-3 for color filters for organic EL display devices.

[0211] [Example 4] Except for changing the colorant V32-1 used in Example 3 to V32-2, the pigment was micronized in the same manner as in Example 3 to produce colorant V32-4 for color filters for organic EL display devices.

[0212] [Example 5] 147 parts of the colorant V32-1 produced in Example 1, 3 parts of the compound represented by formula (1), 1500 parts of sodium chloride, and 230 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50°C for 6 hours. Next, this mixture was added to 6000 parts of hot water and stirred for 2 hours while heating to 80°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to produce colorant V32-5 for color filters for organic EL display devices.

[0213] [Example 6] 143 parts of the colorant V32-1 produced in Example 1, 7 parts of the compound represented by formula (1), 1500 parts of sodium chloride, and 230 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50°C for 6 hours. Next, this mixture was added to 6000 parts of hot water and stirred for 2 hours while heating to 80°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to produce colorant V32-6 for color filters for organic EL display devices.

[0214] [Example 7] 137 parts of the colorant V32-1 produced in Example 1, 13 parts of the compound represented by formula (1), 1500 parts of sodium chloride, and 230 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50°C for 6 hours. Next, this mixture was added to 6000 parts of hot water and stirred for 2 hours while heating to 80°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to produce colorant V32-7 for color filters for organic EL display devices.

[0215] [Comparative Example 1] The colorant V32-1 produced in Example 1 was dispersed in 100 parts and 1000 parts of N,N-dimethylformamide and stirred for 2 hours. After filtration and washing with water, the resulting wet cake was dried overnight at 80°C to produce colorant V32-8 for color filters for organic EL display devices.

[0216] [Comparative Example 2] Except for changing the colorant V32-1 used in Example 3 to V32-8, the pigment was micronized using the same method as in Example 3 to produce the colorant V32-9 for color filters for organic EL display devices.

[0217] [Comparative Example 3] 133 parts of the colorant V32-1 produced in Example 1, 17 parts of the compound represented by formula (1), 1500 parts of sodium chloride, and 230 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50°C for 6 hours. Next, this mixture was added to 6000 parts of hot water and stirred for 2 hours while heating to 80°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to produce colorant V32-10 for color filters for organic EL display devices.

[0218] For the obtained colorants for organic EL display devices, the content of the compound represented by formula (1) relative to the total amount of CI pigment violet 32 ​​and the compound represented by formula (1), and the average primary particle size of the colorant were measured. The measurement method is as follows. The results obtained are shown in Table 1.

[0219] (Method for measuring the compound represented by formula (1)) 80 mg of a colorant for color filters used in organic EL display devices was accurately weighed into a sample bottle, 10 ml of methanol was added, and the mixture was dispersed in an ultrasonic cleaner for 1 hour. The dispersion was filtered through a 0.2 μm membrane filter and used as a sample. The results of the analysis performed by high-performance liquid chromatography under the following conditions are summarized in Table 1. Equipment: High-performance liquid chromatograph "2695 Separation Module" manufactured by Waters Japan. Injection volume: 3μl Detector: PDA 240nm Eluent: methanol / ammonium phosphate buffer Flow rate: 0.5ml / min Temperature: 35℃ Calibration curve: A calibration curve was created using the compound represented by equation (1).

[0220] (Method for measuring the average primary particle size of colorants) The average primary particle diameter of the colorant was determined by the average value of approximately 200 particles arbitrarily selected from images measured using a Hitachi High-Technologies Corporation TEM (Transmission Electron Microscope) H-7650. When particles had both a long axis and a short axis, the length of the long axis was used.

[0221] [Table 1]

[0222] <Manufacturing of colored compositions for color filters in organic EL display devices> [Example 101] (Coloring composition 101) After stirring and mixing the following mixture until homogeneous, it was dispersed for 3 hours using 0.5 mm diameter zirconia beads in an Eiger mill (Eiger Japan's "Mini Model M-250MKII"), and then filtered through a 5.0 μm pore size filter to produce colored composition 1 with 20% by mass of nonvolatile components. Details of the raw materials used will be described later. PV32-1: 5.0 copies PR264: 6.3 copies PY139: 1.3 parts Pigment derivative 1:0.7 parts Pigment derivative 2:0.7 parts Resin (B1-1) solution (50% solids): 12.0 parts Propylene glycol monomethyl ether acetate: 74.0 parts

[0223] [Examples 102-136, Comparative Examples 101-103] (Coloring composition 102~139) Colored compositions 102 to 139 were manufactured in the same manner as colored composition 101, except that the colorants and resins were changed to the raw materials listed in Table 2. Regarding the colorants, the amount of colorants other than pigment derivatives was adjusted so that x=0.697 and y=0.301 with a C light source. However, the total amount of colorants other than pigment derivatives was 12.6 parts.

[0224] <Evaluation of coloring compositions for color filters in organic EL display devices> The following procedure was used to evaluate coloring compositions for color filters in organic EL display devices. The results are shown in Table 2.

[0225] (coloring power) The obtained colored composition was applied to a 100 mm x 100 mm, 1.1 mm thick glass substrate using a spin coater. Then, it was dried at 60°C for 5 minutes, followed by heating at 100°C for 20 minutes, and then allowed to cool to produce a coated substrate. The coated substrate was heat-treated at 100°C and then adjusted to a chromaticity of x=0.697 and y=0.301 using a C light source. For the obtained coated film substrate, the film thickness of the coated film was measured using a surface shape measuring device "Dektak8 (manufactured by Veeco)" and evaluated according to the following criteria. The thinner the film thickness, the higher the coloring power. ◎: Film thickness is less than 2.0 μm 〇: Film thickness is 2.0 μm or more and less than 2.2 μm △: Film thickness is 2.2 μm or more and less than 2.4 μm ×: Film thickness is 2.4 μm or more

[0226] (Reflectance) Using the same coated film substrate as for the coloring power evaluation, the reflectance of the coated film was measured using a spectrophotometric color system "CM-26D (manufactured by Konica Minolta)" and evaluated according to the following criteria. In the measurement, a black film tape (manufactured by Chuo Shing Chemical Industry Co., Ltd.) was attached to the coated surface of the coated film substrate, with the tape-attached surface facing down and the glass surface facing up, and light was applied from the glass surface for measurement. The lower the SC, the lower the reflectance. ◎: SC is less than 5.5 〇: SC is 5.5 or more and less than 5.7 △: SC is 5.7 or more and less than 6.0 ×: SC is 6.0 or more

[0227] (Solvent resistance) Using the same coated film substrate as for the coloring power evaluation, the chromaticity of the coated film under a C light source ([L * (1), a * (1), b * (1)]) was measured using a micro spectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). Subsequently, the substrate was immersed in propylene glycol monomethyl ether acetate for 5 minutes, then the substrate was taken out and the propylene glycol monomethyl ether acetate was removed with air, and then the chromaticity of the coated film under a C light source ([L * (2), a <着 * (2), b * (2)]) was measured, and the color difference ΔEab * was obtained and evaluated according to the following criteria. ΔEab * = √((L * (2)- L * (1)) 2 + (a * (2)-a * (1)) 2 +( b * (2)- b * (1)) 2 ) ◎:ΔEab * is less than 1.0 〇:ΔEab * The value is between 1.0 and 1.5. △:ΔEab * The value is between 1.5 and 3.0. ×:ΔEab * 3.0 or higher

[0228] <Ingredients listed in the table> The raw materials listed in Table 2 below are as follows:

[0229] (Other colorants) PR264: CI Pigment Red 264 PR177: CI Pigment Red 177 PR179: CI Pigment Red 179 PR269: CI Pigment Red 269 PR122: CI Pigment Red 122 PY139: CI Pigment Yellow 139 PY185: CI Pigment Yellow 185 PY150: CI Pigment Yellow 150 PY138: CI Pigment Yellow 138

[0230] (Pigment derivatives) Pigment derivatives 1-4: Structure shown below [ka]

[0231] [Table 2]

[0232] As shown in Table 2, the colored compositions of the examples were able to form films with high coloring power, low reflectivity, and excellent solvent resistance during low-temperature curing.

[0233] <Manufacturing of photosensitive colored compositions for color filters in organic EL display devices> [Example 201] (Photosensitive coloring composition 1) A mixture of the following compositions was stirred and mixed until homogeneous, and then filtered through a 1 μm pore size filter to produce photosensitive colored composition 1. Coloring composition 101 (solid content 20%): 37.50 parts Resin (B3) solution (50% solids): 6.85 parts Photopolymerizable compound (Aronix M-402, manufactured by Toagosei Co., Ltd.): 3.75 parts Photopolymerization initiator (ADEKA "ADEKA Cruise NIC-831"): 0.23 parts Leveling agent (2% solid content, see below): 5.00 parts Propylene glycol monomethyl ether acetate: 46.68 parts

[0234] The leveling agent mentioned above is as follows: A leveling agent was prepared by mixing 1 part each of BYK-330 (manufactured by Big Chemie) and Megafac F-551 (manufactured by DIC), dissolving them in 98 parts of PGMAc to create a mixed solution.

[0235] [Examples 202-236, Comparative Examples 201-203] (Photosensitive coloring composition 2-39) Photosensitive colored compositions 2 to 39 were manufactured in the same manner as in the manufacture of photosensitive colored composition 1, except that colored composition 101 was changed to one of the colored compositions listed in Table 3.

[0236] <Evaluation of photosensitive colored compositions for color filters in organic EL display devices> The photosensitive colored compositions were evaluated using the following procedure. The results are shown in Table 3.

[0237] (coloring power) The obtained photosensitive colored composition was applied to a 100 mm × 100 mm, 1.1 mm thick glass substrate using a spin coater, dried at 70°C for 20 minutes, exposed to ultraviolet light at an integrated light intensity of 100 mJ / cm2 using an ultra-high pressure mercury lamp, and developed with an alkaline developer at 23°C to obtain a coated substrate. Then, it was heated at 100°C for 20 minutes and allowed to cool. The thickness of the coating film on the obtained coated substrate was measured using a surface shape measuring device "Dektak8 (manufactured by Veeco)" and evaluated according to the following criteria. The thinner the film thickness, the higher the coloring power. The coated substrate was heat-treated at 100°C and adjusted to a chromaticity of x=0.697 and y=0.301 using a C light source. The alkaline developer used consisted of 1.5% by mass of sodium carbonate, 0.5% by mass of sodium bicarbonate, 8.0% by mass of anionic surfactant (Kao Corporation's "Perilex NBL"), and 90% by mass of water. ◎: Film thickness less than 3.5 μm ○: Film thickness of 3.5 μm or more, and less than 3.8 μm. △: Film thickness is 3.8 μm or more, but less than 4.0 μm. ×: Film thickness is 4.0 μm or more

[0238] (reflectance) Using the same coating substrate as for the color strength evaluation, the reflectance of the coating was measured using the spectrophotometric system "CM-26D (manufactured by Konica Minolta)" and evaluated according to the following criteria. For the measurement, a black film tape (manufactured by Chuko Kasei Kogyo Co., Ltd.) was attached to the coated surface of the coated substrate, with the tape-attached side facing down and the glass side facing up, and the measurement was performed by shining light from the glass side. The lower the SC (Sensitivity), the lower the reflectivity. ◎: SC is less than 5.5 ○: SC is 5.5 or higher, but less than 5.7 △: SC is 5.7 or higher, but less than 6.0 ×: SC is 6.0 or higher

[0239] (Solvent resistance) Using the same coated film substrate as for color strength evaluation, the chromaticity of the coating film under a C light source ([L * (1), a * (1), b * (1)) was measured using a micro-spectrophotometer (Olympus Optical Co., Ltd. "OSP-SP100"). Subsequently, the substrate was immersed in propylene glycol monomethyl ether acetate for 5 minutes, then the substrate was removed and the propylene glycol monomethyl ether acetate was removed with air, and the chromaticity ([L) was measured using a C light source. * (2), a * (2), b * (2)) is measured, and the color difference ΔEab is calculated using the following formula. * We sought and evaluated the following criteria. ΔEab * = √((L * (2)- L * (1)) 2 + (a * (2)-a * (1)) 2 +( b * (2)- b * (1)) 2 ) ◎:ΔEab * is less than 1.0 〇:ΔEab * The value is between 1.0 and 1.5. △:ΔEab * The value is between 1.5 and 3.0. ×:ΔEab * 3.0 or higher

[0240] [Table 3]

[0241] As shown in Table 3, the photosensitive coloring compositions of the examples were able to form films with high coloring power, low reflectivity, and excellent solvent resistance during low-temperature curing.

[0242] In the photosensitive colored compositions of each example, the same effects as in each example can be obtained even if the compound described in <Photopolymerizable Compound (C)> above is included in an amount of 1 to 50% by mass of 100% by mass of the nonvolatile content of the photosensitive colored composition, and the compound described in <Photopolymerization Initiator (D)> above is included in an amount of 0.1 to 20% by mass of 100% by mass of the nonvolatile content of the colored composition.

[0243] In the photosensitive colored compositions of each example, the same effects as in each example can be obtained even if two or more types of photopolymerizable compounds and photopolymerization initiators are used in combination.

[0244] As described above, the coloring composition of the present invention has high coloring power, low reflectivity, and can form a film with excellent solvent resistance during low-temperature curing, making it suitable for manufacturing color filters for organic EL display devices.

Claims

1. A coloring agent for color filters for organic EL display devices, comprising C.I. Pigment Violet 32 ​​and a compound represented by the following formula (1), wherein the content of the compound represented by the following formula (1) is 0.01 to 10.0% by mass relative to the total amount of C.I. Pigment Violet 32 ​​and the compound represented by the following formula (1). Formula (1) 【Chemistry 1】

2. A coloring agent (A) comprising the coloring agent for color filters for organic EL display devices described in claim 1, A coloring composition for color filters for organic EL display devices, comprising resin (B).

3. The coloring composition for a color filter for an organic EL display device according to claim 2, wherein the resin (B) comprises a resin-type dispersant (B1) having an aromatic carboxyl group.

4. The coloring composition for a color filter for an organic EL display device according to claim 2, wherein the resin (B) comprises a resin-type dispersant (B2) having a basic substituent.

5. The coloring composition for a color filter for an organic EL display device according to claim 2, wherein the coloring agent (A) comprises a pigment derivative having a basic substituent.

6. Furthermore, the coloring composition for a color filter for an organic EL display device according to claim 2, comprising a photopolymerizable compound (C) and / or a photopolymerizable initiator (D).

7. A film formed from a coloring composition for a color filter for an organic EL display device according to claim 2 or 6.

8. A color filter having the film described in claim 7.

9. An organic EL display device comprising the color filter described in claim 8.

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