Coloring composition for color filters, color curable composition for color filters, color filters, solid-state image sensors, and image display devices.

Abstract

To provide a colored composition for color filters that exhibits high contrast ratio due to low aggregation of pigments, fewer film defects in the coating even after long-term storage under temperature fluctuations, and good pattern characteristic dependence with respect to the time from application to exposure when used as a colored curable composition. To provide a colored curable composition for color filters, a color filter, a solid-state image sensor, and an image display device using the colored composition for color filters. [Solution] A coloring composition for color filters comprising a pigment (A), a dye derivative (B), a resin-type dispersant (C), and an organic solvent (D), wherein the dye derivative (B) comprises a compound having a heterocycle (B1), a compound having a heterocycle (B2), and a compound having a heterocycle (B3), and the mass ratio of compounds (B1) to (B3) satisfies a specific range.

Description

Technical Field

[0001] The present invention relates to a coloring composition, a coloring curable composition, a color filter, a solid-state imaging device including the color filter, and an image display device, which are used for manufacturing a color filter used in an image display device such as a liquid crystal display device (liquid crystal television) and a solid-state imaging device (CCD, CMOS, etc.).

Background Art

[0002] In recent years, due to the spread of liquid crystal display devices, organic EL display devices, digital cameras, smartphones, infrared sensors, etc., the demand for color filters used in these devices has been increasing. A color filter decomposes incident light into colors, and the colors are synthesized to form an image. Therefore, high brightness, high contrast, and color reproducibility are required for color filters.

[0003] In addition, as quality items required for coloring compositions and coloring curable compositions used for forming color filters, the importance of filtration properties and quality stability during long-term storage under temperature fluctuations has also increased. In the production of coloring compositions for color filters, there is a filtration step in the final process. However, if coarse particles remain, the filtration filter must be frequently replaced, resulting in a significant reduction in the filtration processing speed. Furthermore, customers who want to reduce the risk of failures in production lines and cold storages require quality stability during long-term storage under temperature fluctuations.

[0004] Generally, pigments or dyes are used for color filters. However, many pigments for achieving high brightness, high contrast, and color reproducibility have fine primary particles. In particular, pigments used for color filters are often further refined compared to conventional pigments in order to improve the contrast ratio of the coating film. Known methods for preparing fine pigment particles include the acid pesto method, which involves dissolving the pigment in an acid such as sulfuric acid or phosphoric acid, and then injecting an aqueous sulfuric acid solution into water to precipitate it. Another known method is the solvent-salt milling method, which involves mechanically kneading a mixture containing the pigment, a water-soluble inorganic salt, and a water-soluble organic solvent.

[0005] Such pigments are aggregates of primary particles, and in order to bring out the properties of the pigment itself, it is necessary to disperse them from the aggregated state to a finer state. However, generally, the finer the pigment particles, the more difficult it is to disperse them uniformly. Dispersions with poor dispersion are often highly viscous, making them difficult to handle in terms of dispersion and transport, and in some cases, they may gel, drastically reducing their filterability. Furthermore, they are easily affected by temperature fluctuations, which can lead to film defects when used in coatings.

[0006] Furthermore, when forming color filters used in liquid crystal display elements, solid-state image sensors, and organic EL display devices, the process typically involves applying a color-curable composition to a substrate, followed by pattern exposure and development with an alkaline developer. During this process, a delay of several days may occur between the application of the color-curable composition and the exposure / development process. This post-coating delay is generally called PCD (Post Coating Delay). This is because, in the color filter manufacturing process, it can be more efficient to store substrates coated with the color-curable composition and perform the next exposure / development process in batches as soon as the exposure / development equipment becomes available. Given this background, color-curable compositions are required to not cause problems in the formation of color patterns even after PCD.

[0007] It is known that using various derivatives having a pigment skeleton or a similar structure is effective in achieving a uniform dispersion of fine primary pigment particles. To date, various structures have been disclosed, including pigment derivatives in which functional groups such as acidic groups, basic groups, and phthalimidomethyl groups have been introduced into the pigment skeleton, and pigment derivatives in which the pigment skeleton is bonded to a part of the resin. These have long been used in applications such as dispersants, particle growth inhibitors, and crystal transition inhibitors.

[0008] Such dye derivatives are disclosed in Patent Documents 1 to 3, and all are used in colored curable compositions such as resist inks for color filters. While all of these have the effect of improving the dispersion state, they do not have sufficient properties to prepare pigment dispersions with finer dispersion particle size, good filterability, long-term storage stability under temperature fluctuations, and good pattern property dependence on PCD. [Prior art documents] [Patent Documents]

[0009] [Patent Document 1] Japanese Patent Publication No. 2017-146350 [Patent Document 2] Japanese Patent Publication No. 2017-191152 [Patent Document 3] Japanese Patent Publication No. 2022-166873 [Overview of the Initiative] [Problems that the invention aims to solve]

[0010] The present invention provides a colored composition for color filters that exhibits a high contrast ratio due to the low likelihood of pigment aggregation, good filterability, few film defects in the coating even after long-term storage under temperature fluctuations, and good pattern characteristic dependence (hereinafter also simply referred to as "PCD dependence") on the time from application to exposure (long exposure time) (PCD: Post Coating Delay) when used as a colored curable composition. The present invention also provides a colored curable composition for color filters, a color filter, a solid-state image sensor, and an image display device using the colored composition for color filters. [Means for solving the problem]

[0011] The inventors conducted diligent research and discovered that the above problems could be solved by incorporating a pigment derivative with a specific structure in a specific mass ratio, leading to the present invention.

[0012] In other words, embodiments of the present invention relate to a colored composition for color filters comprising a pigment (A), a dye derivative (B), a resin-type dispersant (C), and an organic solvent (D), wherein the dye derivative (B) comprises a compound (B1) having a heterocycle represented by the following general formula (1), a compound (B2) having a heterocycle represented by the following general formula (2), and a compound (B3) having a heterocycle represented by the following general formula (3), and the mass ratio of compounds (B1) to (B3) satisfies the range of the following formulas [1] to [3]. [1] (B1) / ((B1)+(B2)+(B3))=80.0~99.0% [2] (B2) / ((B1)+(B2)+(B3))=0.5~10.0% [3] (B3) / ((B1)+(B2)+(B3))=0.5~10.0% General formula (1) [ka] In general formula (1), R1 to R9 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent. X1 represents -NHSO2- or -NHCO-, X2 represents an alkylene group which may have a substituent, an arylene group which may have a substituent, or a heterocyclic residue which may have a substituent, and X3 represents -NH- or -O-. A and B each independently represent -O-(CH2)n-R 14 , -OR 12 , -NR 13 R 14 , -Cl, -F, -Y1-Y2-NR 15 R 16 and represent a group selected from. R 11 represents a heterocyclic residue which may have a substituent, and R 12 to 14 each independently represent a hydrogen atom, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent. Y1 represents -NH- or -O-, and Y2 represents an alkylene group which may have a substituent or an arylene group which may have a substituent. R 15 and R 16 each independently represent an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent. R 15 and R 16 may combine together to form a heterocyclic structure which may contain an additional nitrogen atom, oxygen atom or sulfur atom and may be substituted. Either A or B is -O-(CH2) n -R 11 , -OR 12 , -NR 13 R 14 , or -Y1-Y2-NR 15 ​​​​​​​​​​ [In general formula (2), R 21 ~R 25 Each of these independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxy group. 26 X represents a methyl group. X4 represents -NHSO2- or -NHCO-, X5 represents an optionally substituted alkylene group, an optionally substituted arylene group, or an optionally substituted heterocyclic residue, and X6 represents -NH- or -O-. A and B represent those defined in general formula (1), and either A or B is -O-(CH2) n -R 11 , -OR 12 , -NR 13 R 14 , or -Y1-Y2-NR 15 R 16 That is the case. General formula (3) [ka] [In general formula (3), R 41 ~ 44 , R 46 ~ 50 Each of these independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxy group. 45 X represents a carboxyl group. X7 represents -NHSO2- or -NHCO-, X8 represents an optionally substituted alkylene group, an optionally substituted arylene group, or an optionally substituted heterocyclic residue, and X9 represents -NH- or -O-. A and B represent those defined in general formula (1), and either A or B is -O-(CH2) n -R 11 , -OR 12 , -NR 13 R14 , or -Y1-Y2-NR 15 R 16 That is the case.

[0013] Furthermore, embodiments of the present invention relate to a colored composition for color filters, characterized in that the resin-type dispersant (C) includes an acidic resin-type dispersant having an aromatic carboxyl group.

[0014] Furthermore, embodiments of the present invention relate to a colored curable composition for color filters, characterized by comprising the colored composition for color filters, a photopolymerization initiator (E), and a photopolymerizable compound (F).

[0015] Furthermore, embodiments of the present invention relate to a color filter characterized by comprising a filter segment formed from the colored composition for color filters or the colored curable composition for color filters.

[0016] Furthermore, embodiments of the present invention relate to a solid-state image sensor characterized by comprising the color filter.

[0017] Furthermore, embodiments of the present invention relate to an image display device characterized by comprising the color filter. [Effects of the Invention]

[0018] According to the present invention, a colored composition for color filters is provided that has a high contrast ratio, good filterability, few film defects even when stored for a long period of time under temperature fluctuations, and good pattern characteristic dependence on long-term storage when used as a colored curable composition. Furthermore, a colored curable composition for color filters, a color filter, a solid-state image sensor, and an image display device using the same can be provided. [Modes for carrying out the invention]

[0019] The present invention will be described in detail below. In this specification, "CI" refers to the color index number. Furthermore, when "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" are written, unless otherwise specified, they refer to "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively.

[0020] <<Coloring composition for color filters>> The colored composition for color filters of the present invention is characterized by comprising a pigment (A), a dye derivative (B), a resin-type dispersant (C), and an organic solvent (D), as described below.

[0021] <Pigment (A)> The present invention relates to a colored composition for color filters, characterized by containing a pigment (A) as a coloring agent. Any conventionally known pigment can be used as pigment (A).

[0022] Specifically, as red pigments, for example, CIPigment 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, 63:1, 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, 20 0, 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, 263, 264, 265, 266, 267, 268, 269, 270, 27 Examples include 1, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, anthraquinone pigments represented by general formula (6), diketopyrrolopyrrole pigments described in Japanese Patent Publication No. 2011-523433, azo pigments described in Japanese Patent Application Publication No. 2014-112527, and azo pigments described in Japanese Patent Application Publication No. 2013-161026. Among these, CIPigment Red 177, 179, 242, 254, 272, and 291 are particularly preferred.

[0023] Examples of orange pigments include CIPigment Orange 36, 38, 43, 51, 55, 59, 61, 71, and 73. Among these, CIPigment Orange 36, 38, 71, and 73 are particularly preferred.

[0024] Examples of yellow pigments include CIPigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 12 Examples include 3, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, 231, and 233. Among these, CIPigment Yellow 138, 139, 150, 185, 231, and 233 are particularly preferred.

[0025] Examples of green pigments include CIPigment Green 7, 36, 58, 59, 62, or 63. Among these, CIPigment Green 58, 59, 62, and 63 are particularly preferred.

[0026] Examples of blue pigments include CIPigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, or 79. Among these, CIPigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 are particularly preferred.

[0027] Examples of purple pigments include 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, 32, 37, 39, 42, 44, 47, 49, and 50.

[0028] In addition, examples of inorganic pigments include 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.

[0029] The coloring composition for color filters of the present invention may also contain dyes as coloring agents, to the extent that it does not impair the effects of the invention. Any of the following dyes can be used: acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Derivatives of these dyes, or in the form of lake pigments (dyes prepared by lake formation), are also acceptable.

[0030] These pigments and dyes can be used individually or in combination of two or more.

[0031] <Dye derivative (B)> The present invention relates to a coloring composition for color filters in which the dye derivative (B) comprises a compound (B1) having a heterocycle represented by the following general formula (1), a compound (B2) having a heterocycle represented by the following general formula (2), and a compound (B3) having a heterocycle represented by the following general formula (3), wherein the mass ratio of compounds (B1) to (B3) satisfies the range of formulas [1] to [3] described later. Hereinafter, compounds having a heterocycle represented by general formula (1) (B1), compounds having a heterocycle represented by general formula (2) (B2), and compounds having a heterocycle represented by general formula (3) (B3) may simply be referred to as compounds (B1), (B2), and (B3). [1] (B1) / ((B1)+(B2)+(B3))=80.0~99.0% [2] (B2) / ((B1)+(B2)+(B3))=0.5~10.0% [3] (B3) / ((B1)+(B2)+(B3))=0.5~10.0%

[0032] General formula (1) [ka]

[0033] In general formula (1), R1 to R9 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxy group. X1 represents -NHSO2- or -NHCO-, X2 represents an optionally substituted alkylene group, an optionally substituted arylene group, or an optionally substituted heterocyclic residue, and X3 represents -NH- or -O-. Among these, R1 to R4 are preferably halogen atoms, and R5 to R9 are preferably hydrogen atoms. X1 is preferably -NHSO2-, X2 is preferably C6H4, and X3 is preferably -NH-.

[0034] A and B are independently -O-(CH2) n -R 11 , -OR 12 , -NR 13 R 14 -Cl, -F, -Y1-Y2-NR 15 R 16 It represents the base selected from among them. R 11 R represents a heterocyclic residue which may have substituents. 12 ~ 14 Each independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxy group. Y1 represents -NH- or -O-, and Y2 represents an optionally substituted alkylene group or an optionally substituted arylene group. 15 and R 16Each of these independently represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxy group. 15 and R 16 These may combine to form a heterocyclic structure that may contain and be substituted with further nitrogen, oxygen, or sulfur atoms. Either A or B is -O-(CH2) n -R 11 , -OR 12 , -NR 13 R 14 , or -Y1-Y2-NR 15 R 16 That is the case. Among these, A and B are -NH-Y2-NR 15 R 16 Preferably, R 15 and R 16 An ethyl group is preferred.

[0035] General formula (2) [ka]

[0036] In general formula (2), R 21 ~R 25 Each of these independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxy group. 26 X represents a methyl group. X4 represents -NHSO2- or -NHCO-, X5 represents an optionally substituted alkylene group, an optionally substituted arylene group, or an optionally substituted heterocyclic residue, and X6 represents -NH- or -O-. Among these, R 21 ~R 25 X4 is preferably a hydrogen atom, X4 is preferably -NHSO2-, X5 is preferably C6H4, and X6 is preferably -NH-. Among these, A and B are -NH-Y2-NR 15 R 16 Preferably, R 15 and R16 An ethyl group is preferred.

[0037] General formula (3)

Chemical formula

[0038] In general formula (3), R 41 ~ 44 and R 46 ~ 50 each independently represent a hydrogen atom, a halogen atom, a hydroxyl group, an alkyl group which may have a substituent, an aryl group which may have a substituent, or an alkoxy group which may have a substituent. R 45 represents a carboxyl group. X7 represents -NHSO2- or -NHCO-, X8 represents an alkylene group which may have a substituent, an arylene group which may have a substituent, or a heterocyclic residue which may have a substituent, and X9 represents -NH- or -O-. Among these, R[[ID=​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​​Examples of alkyl groups that may have substituents include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, tert-butyl group, isobutyl group, tert-amyl group, 2-ethylhexyl group, stearyl group, chloromethyl group, trichloromethyl group, trifluoromethyl group, 2-methoxyethyl group, 2-chloroethyl group, 2-nitroethyl group, cyclopentyl group, cyclohexyl group, and dimethylcyclohexyl group, among which methyl group and trifluoromethyl group are preferred.

[0041] Examples of aryl groups that may have substituents include phenyl group, naphthyl group, 4-methylphenyl group, 3,5-chlorophenyl group, 4-chloro-2-methylphenyl group, 4-tert-butylphenyl group, 4-methoxyphenyl group, 4-diethylaminophenyl group, and 4-nitrophenyl group, among which the phenyl group is preferred.

[0042] Examples of alkoxy groups that may have substituents include methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, n-octyloxy, 2-ethylhexyloxy, trifluoromethoxy, cyclohexyloxy, stearyloxy, and 2-(diethylamino)ethoxy groups, among which methoxy and trifluoromethoxy groups are preferred.

[0043] The optionally substituted alkylene group and optionally substituted arylene group can be defined as a group obtained by removing one hydrogen atom from the optionally substituted alkyl group and optionally substituted aryl group, and among these, the methylene group and the phenylene group are preferred.

[0044] Examples of heterocyclic residues that may have substituents include pyridine, methylpyridine, indole, and quinoline, with indole and quinoline being preferred among these.

[0045] In the present invention, by using a main component compound (B1) and compounds (B2) and (B3) having similar structures in a specific mass ratio as the dye derivative (B), it is possible to provide a pigment composition that has a higher contrast ratio, fewer film defects under temperature fluctuations, and better PCD dependence compared to when conventionally known derivatives are used. The reason for this is not yet clear, but the inventors consider the following.

[0046] Colored compositions for color filters are created by mixing resins, solvents, polymerizable compounds, etc., to form a colored, curable composition for color filters, which is then applied to substrates such as glass substrates. The resins and solvents added at this time are selected from compounds with various polarities and physical properties depending on the required function.

[0047] On the other hand, in the case of compounds with relatively large molecular weights, such as compound (B1), the affinity with resins and solvents is not good, resulting in poor compatibility and insufficient adsorption between the dye derivative and the resin. As a result, it is thought that the storage stability under temperature fluctuations deteriorates when used as a colored composition for color filters, and the PCD dependence deteriorates when used as a colored curable composition. Here, we consider that by using small amounts of compounds (B2) and (B3) in combination, the compatibility with various resins and solvents is improved due to the difference in affinity and the effect of polar groups, and the adsorption between the dye derivative and the resin is promoted, thereby improving the storage stability under temperature fluctuations and the PCD dependence.

[0048] The dye derivative (B) used in the colored composition for color filters of the present invention is characterized in that the mass ratio of the heterocyclic compounds (B1), (B2), and (B3) described above satisfies the range of the following formulas [1] to [3]. [1] (B1) / ((B1)+(B2)+(B3))=80.0~99.0% [2] (B2) / ((B1)+(B2)+(B3))=0.5~10.0% [3] (B3) / ((B1)+(B2)+(B3))=0.5~10.0%

[0049] The range of equations [1] to [3] is more preferably as follows: [1] (B1) / ((B1)+(B2)+(B3))=90.0~99.0% [2] (B2) / ((B1)+(B2)+(B3))=0.5~5.0% [3] (B3) / ((B1)+(B2)+(B3))=0.5~5.0% By setting the mass ratio of the heterocyclic compounds (B1), (B2), and (B3) within the above range, a composition with a higher contrast ratio, fewer film defects under temperature fluctuations, and good PCD dependence can be obtained.

[0050] The synthesis method for the heterocyclic compounds (B1), (B2), and (B3) is not particularly limited, but examples include the method disclosed in Production Example 6 of Japanese Patent Application Publication No. 2006-291194, or a method in which the raw materials are changed as necessary from the said publication. Compound (B3) can also be obtained by hydrolyzing compound (B1) by an appropriate method. If the synthesized compounds contain impurities, they may be removed by recrystallization, reprecipitation, filtration, washing, or preparative liquid chromatography.

[0051] The following are specific examples of the structures of compounds (B1), (B2), and (B3) having heterocycles, but the present invention is not limited to these examples.

[0052] Compounds containing heterocycles (B1) [ka] JPEG2026111386000008.jpg136170JPEG2026111386000009.jpg134170JPEG2026111386000010.jpg150170JPEG2026111386000011.jpg51170

[0053] Compounds containing heterocycles (B2) [ka] JPEG2026111386000013.jpg127170 JPEG2026111386000014.jpg133170JPEG2026111386000015.jpg35170

[0054] Compounds containing heterocycles (B3) [ka] JPEG2026111386000017.jpg138170 JPEG2026111386000018.jpg150170 JPEG2026111386000019.jpg171170 JPEG2026111386000020.jpg53170

[0055] The heterocyclic compounds (B1), (B2), and (B3) are preferably added in a total of 1 to 100 parts by mass, and more preferably 5 to 30 parts by mass, per 100 parts by mass of pigment.

[0056] Furthermore, in addition to the dye derivative (B), conventionally known dye derivatives may be added to the coloring composition for color filters of the present invention. Specifically, diketopyrrolopyrrole dye derivatives include Japanese Patent Publication No. 2001-220520, WO2009 / 081930, WO2011 / 052617, WO2012 / 102399, and Japanese Patent Publication No. 2017-156397; phthalocyanine dye derivatives include Japanese Patent Publication No. 2007-226161, WO2016 / 163351, Japanese Patent Publication No. 2017-165820, and Japanese Patent No. 5753266; and anthraquinone dye derivatives include For example, see Japanese Patent Publication No. 63-264674, Japanese Patent Publication No. 09-272812, Japanese Patent Publication No. 10-245501, Japanese Patent Publication No. 10-265697, Japanese Patent Publication No. 2007-079094, Brochure WO2009 / 025325, as quinacridone-based dye derivatives, see Japanese Patent Publication No. 48-54128, Japanese Patent Publication No. 03-9961, Japanese Patent Publication No. 2000-273383, as dioxazine-based dye derivatives, see Japanese Patent Publication No. 2011-162662, as thiaidine-indigo-based dye derivatives, see Japanese Patent Publication No. 2007 -Publication No. 314785, as triazine-based dye derivatives, Japanese Patent Publication No. 61-246261, Japanese Patent Publication No. 11-199796, Japanese Patent Publication No. 2003-165922, Japanese Patent Publication No. 2003-168208, Japanese Patent Publication No. 2004-217842, Japanese Patent Publication No. 2007-314681, as benzoisoindole-based dye derivatives, Japanese Patent Publication No. 2009-57478, as quinophthalone-based dye derivatives, Japanese Patent Publication No. 2003-167112, Japanese Patent Publication No. 2008-31281, Japanese Patent Publication No. 2012-22611 Examples of known dye derivatives include those described in Japanese Patent Publication No. 0, Japanese Patent Publication No. 2012-208329 and Japanese Patent Publication No. 2014-5439 as naphthol-based dye derivatives, Japanese Patent Publication No. 2001-172520 and Japanese Patent Publication No. 2012-172092 as azo-based dye derivatives, Japanese Patent Publication No. 2004-307854 as acidic substituents, and Japanese Patent Publication No. 2002-201377, Japanese Patent Publication No. 2003-171594, Japanese Patent Publication No. 2005-181383 and Japanese Patent Publication No. 2005-213404 as basic substituents.In these documents, dye derivatives may be described as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds, but compounds having substituents such as acidic groups, basic groups, or neutral groups on organic dye residues are synonymous with dye derivatives.

[0057] These dye derivatives can be used individually or in combination of two or more types.

[0058] <Pigment miniaturization> When using an organic pigment as pigment (A), it can be used after being micronized using conventionally known methods. It is preferable to mix the organic pigment with other raw materials after micronization. Examples of micronization methods include wet grinding, dry grinding, and dissolution extraction. Among these, solvent salt milling, a type of wet grinding, or acid pasting, a type of dissolution extraction, is preferred. The average primary particle size of the organic pigment after micronization is preferably 10 to 80 nm, and more preferably 15 to 70 nm. A suitable particle size further improves dispersibility and the contrast ratio of the coating. The average primary particle size is the average value of approximately 20 particles arbitrarily selected from a magnified image 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.

[0059] (Solvent-salt milling method) Solvent salt milling is a process in which a mixture of organic pigments, pigment derivatives, water-soluble inorganic salts, and water-soluble organic solvents is mechanically kneaded under heating using a kneader, two-roll mill, three-roll mill, ball mill, attritor, or sand mill, and then washed with water to remove the water-soluble inorganic salts and water-soluble organic solvents. The water-soluble inorganic salts act as crushing aids, and the high hardness of the inorganic salts during salt milling is used to crush the pigment particles. By optimizing the conditions for salt milling the pigments, it is possible to obtain pigments with extremely fine primary particle sizes, a narrow distribution width, a sharp particle size distribution, and a high contrast ratio.

[0060] In the colored composition for color filters of the present invention, an organic pigment may be used as the pigment (A), and a pigment composition may also be used in which a dye derivative (B) containing the heterocyclic compounds (B1) to (B3) represented by the general formulas (1) to (3) described above is mixed with the organic pigment and a solvent salt milling method is applied. The mass ratio of compounds (B1) to (B3) preferably satisfies the range of the following formulas [1] to [3]. [1] (B1) / ((B1)+(B2)+(B3))=80.0~99.0% [2] (B2) / ((B1)+(B2)+(B3))=0.5~10.0% [3] (B3) / ((B1)+(B2)+(B3))=0.5~10.0%

[0061] As water-soluble inorganic salts, sodium chloride, potassium chloride, sodium sulfate, etc., can be used, but sodium chloride (table salt) is preferred from a cost standpoint. From the perspective of both processing efficiency and production efficiency, it is preferable to use 50 to 2000% by mass of the water-soluble inorganic salt, and most preferably 300 to 1000% by mass, based on the total mass of the organic pigment and dye derivative (100% by mass).

[0062] Water-soluble organic solvents serve to wet pigments and water-soluble inorganic salts, and are not particularly limited as long as they dissolve (miscible) in water and do not substantially dissolve the inorganic salt used. However, since the temperature rises during solvent-salt milling and the solvent is prone to evaporation, for safety reasons, solvents with a high boiling point of 120°C or higher are preferred. Examples of such solvents include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, 2-ethyl-1,3-hexanediol, diacetin, triacetin, 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. These water-soluble organic solvents are preferably used in an amount of 5 to 1000% by weight, and most preferably 50 to 500% by weight, based on the total weight (100% by weight) of the organic pigments and dye derivatives.

[0063] During the solvent salt milling process, a resin may be added as needed. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc., can be used. The resin used is preferably water-insoluble, and more preferably partially soluble in the above-mentioned water-soluble organic solvent. The amount of resin used is preferably in the range of 2 to 200% by mass, based on the total mass of the organic pigment and dye derivative (100% by mass).

[0064] The temperature for solvent salt milling is preferably 30°C to 200°C, and more preferably 50°C to 90°C. The mixing time is preferably 1 hour to 48 hours, and more preferably 5 hours to 10 hours. It is preferable to set the temperature and mixing time during solvent salt milling within the above ranges because it results in a higher contrast ratio.

[0065] (Acid pausing method) Acid pasting is a method for producing pigment compositions by co-dissolving organic pigments and dye derivatives in a strongly acidic solvent and then extracting the solution into water. While sulfuric acid, polyphosphate, and chlorosulfonic acid can be used as the strongly acidic solvent, sulfuric acid is preferred industrially from a cost perspective. The concentration of sulfuric acid is not particularly limited, but it is preferably between 50% and 98% by mass, as it is necessary to dissolve the pigments and dye derivatives.

[0066] In the colored composition for color filters of the present invention, an organic pigment can be used as the pigment (A), and a pigment composition can also be used in which an acid paste method is applied to the organic pigment and a dye derivative (B) containing the heterocyclic compounds (B1) to (B3) represented by the general formulas (1) to (3) described above. The mass ratio of compounds (B1) to (B3) preferably satisfies the range of the following formulas [1] to [3]. [1] (B1) / ((B1)+(B2)+(B3))=80.0~99.0% [2] (B2) / ((B1)+(B2)+(B3))=0.5~10.0% [3] (B3) / ((B1)+(B2)+(B3))=0.5~10.0%

[0067] The amount of strong acidic solvent needs to be increased or decreased depending on the concentration of the strong acidic solvent, but is not particularly limited as long as it is an amount that can completely dissolve the organic pigment and / or dye derivative. For example, when using an 80% to 98% by mass aqueous sulfuric acid solution, it is preferable to use 300 to 10000% by weight of the sulfuric acid solution, and more preferably 500 to 3000% by weight, based on the total mass of the organic pigment and dye derivative (100% by mass). The temperature when dissolving the organic pigment and dye derivative in the strong acidic solvent is not particularly limited, but for example, when using an 80% to 98% by mass aqueous sulfuric acid solution, it is preferable to be 0°C or higher and 80°C or lower, and more preferably 5°C or higher and 60°C or lower. The sulfuric acid aqueous solution containing the organic pigment and dye derivative obtained by the above method can be added to a poor solvent such as water to precipitate the dissolved product, filtered and washed to remove acidic components, and then dried and pulverized to obtain a pigment composition.

[0068] In the acid pasting method, there are no particular restrictions on the order in which organic pigments and dye derivatives are added to the strongly acidic solvent; the organic pigment may be added first, the dye derivative first, or both at the same time.

[0069] <Resin-type dispersant (C)> The colored composition for color filters of the present invention can use a known resin-type dispersant (C). The resin-type dispersant (C) can be any dispersant that has a colorant affinity site that has the property of adsorbing to the added colorant and a site that is compatible with the colorant carrier, and that works to stabilize the dispersion on the colorant carrier by adsorbing to the added colorant. Specifically, this includes urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial)amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and variations thereof. Oily dispersants such as amides and their salts formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide adduct compounds, and phosphate ester-based compounds can be used, and these can be used individually or in combination of two or more.

[0070] The resin-type dispersant (C) preferably contains an acidic resin-type dispersant having an aromatic carboxyl group. The acidic resin-type dispersant having an aromatic carboxyl group 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.

[0071] Particularly preferred examples of acidic resin-type dispersants having aromatic carboxyl groups include 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 has a structure having a encapsulation site derived from a monoalcohol, which will be 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. The side chains based on the vinyl polymer moiety are formed by the 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. In this invention, by using an acidic resin-type dispersant having an aromatic carboxyl group, the pigment (A) is efficiently dispersed in the dispersion medium, resulting in a colored composition for color filters with good contrast ratio and film defect properties. Furthermore, by using a colored composition for color filters that is efficiently dispersed in the dispersion medium, a curable colored composition for color filters with good filterability and PCD dependence can be obtained.

[0072] (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.

[0073] (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.

[0074] 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.

[0075] (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.

[0076] The monoalcohol is preferably a compound having an ether group or a carbonyl group. The dispersant may have an ether group or a carbonyl group at the end of its main chain, improving the resolubility of the dispersant in PGMAc. Among these, 3-methoxybutanol, propylene glycol monomethyl ether, and diacetone alcohol are preferred.

[0077] The main chain, which is an aromatic carboxylic acid ester moiety, may have encapsulation sites derived from a monoalcohol, as well as encapsulation sites formed by reaction with water.

[0078] 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.

[0079] (Side chains, which are vinyl polymer components) The side chains of the aforementioned vinyl polymer moiety are obtained by polymerizing a vinyl polymerizable polymerizable compound in the presence of a compound having a thiol group. 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.

[0080] Examples of resin-type dispersants other than acidic resin-type dispersants having aromatic carboxyl groups include, but are not limited to, resin-type dispersants having basic functional groups (basic resin-type dispersants) such as nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles in their side chains, and urethane polymer dispersants.

[0081] Furthermore, as disclosed in Japanese Patent Publication No. 2009-185277, a preferred example is the combined use of an acidic resin-type dispersant having an aromatic carboxyl group and a vinyl resin having a tertiary amino group (which functions as a resin-type dispersant).

[0082] The resin-type dispersant (C) is preferably used in an amount of 3 to 200% by mass relative to the total amount of colorant, and more preferably in an amount of 5 to 100% by mass from the viewpoint of film formation. Furthermore, the acid value is preferably 30-150 mgKOH / g and the weight-average molecular weight (Mw) is preferably 7000-25000, and more preferably the acid value is 60-80 mgKOH / g and the weight-average molecular weight (Mw) is preferably 8000-10000.

[0083] <Organic solvent (D)> The colored composition for color filters of the present invention contains an organic solvent (D) 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 organic solvent (D) is selected considering not only the good coatability of the colored composition for color filters, but also the solubility of each component of the colored composition for color filters, as well as safety.

[0084] As the organic solvent (D), any organic solvent commonly used in this field can be used, and its properties such as boiling point, SP value, evaporation rate, and viscosity should be taken into consideration, and it should be used individually or in mixtures as appropriate according to the application conditions (speed, drying conditions, etc.).

[0085] Examples of organic 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 sulfoxides, and the like.

[0086] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0087] Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxybutanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, anisole, phenethole, and methylanisole.

[0088] Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, ethyl 3-methyl Examples include toxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, dipropylene glycol methyl ether acetate, and dipropylene glycol diacetate.

[0089] Examples of ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0090] Examples of alcoholic solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, and glycerin.

[0091] Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

[0092] Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. These solvents may be used individually or in combination of two or more types.

[0093] 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, cyclohexanone, 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, cyclohexanone, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferred.

[0094] The organic solvent (D) is preferably used in an amount of about 5 to 95% by mass, and more preferably in an amount of about 40 to 90% by mass, relative to the total amount of the coloring composition for the color filter.

[0095] <Binder resin> The colored composition for color filters of the present invention may contain a binder resin. The binder resin is a resin with a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm. Preferably, the transmittance is 95% or more. In terms of curability, examples of binder resins include thermoplastic resins, thermosetting resins, and active energy ray curable resins. The active energy ray curable resin may be a thermoplastic resin or a thermosetting resin that has an active energy ray reactive functional group. In terms of physical properties, the binder resin is preferably an alkali-soluble resin from the viewpoint of developability. Alkali solubility is necessary to provide developability in the alkali development process when manufacturing color filters, and an acidic group is required.

[0096] Binder resins can be used alone or in combination of two or more types.

[0097] The binder resin content is preferably 5 to 400 parts by mass, and more preferably 10 to 250 parts by mass, per 100 parts by mass of colorant. Including an appropriate amount allows for easy film formation and facilitates obtaining good color characteristics.

[0098] (thermoplastic resin) Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclic rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Examples of alkali-soluble thermoplastic resins include resins having acidic groups such as carboxyl groups and sulfone groups. Examples of alkali-soluble thermoplastic resins include acrylic resins having acidic groups, α-olefin / (anhydride) maleic acid copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (anhydride) maleic acid copolymers. Among these, acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers are preferred in terms of improved developability, heat resistance, and transparency.

[0099] (Activated energy ray curable alkali-soluble resin) Active energy ray-curable alkali-soluble resins preferably have ethylenically unsaturated double bonds. Ethyleneenly unsaturated double bonds can be introduced, for example, by the methods (i) and (ii) shown below. The resin undergoes three-dimensional crosslinking due to the effect of active energy rays, which increases the crosslinking density and improves chemical resistance.

[0100] [Method (i)] Method (i) involves, for example, adding a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond to the side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with another monomer. Then, the resulting hydroxyl group is reacted with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group.

[0101] Examples of ethylenically unsaturated monomers having an epoxy group include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acids.

[0102] Examples of unsaturated monobasic acids include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and monocarboxylic acids such as α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted derivatives of (meth)acrylic acid.

[0103] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride. Furthermore, if necessary, such as increasing the number of carboxyl groups, tricarboxylic acid anhydrides such as trimellitic anhydride or tetracarboxylic dianhydrides such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups.

[0104] Other monomers include the following: For example, (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate. Alternatively, examples include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or styrenes such as acryloylmorpholine, or styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and vinyl fatty acid compounds such as vinyl acetate or vinyl propionate.

[0105] Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide Examples include imidobenzoates, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl-6-maleimidehexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimideacridine, and other N-substituted maleimides; EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0106] A method similar to method (i) is, for example, a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with another monomer, to which an ethylenically unsaturated monomer having an epoxy group is added to some of the side chain carboxyl groups of the copolymer, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

[0107] [Method (ii)] Method (ii) involves reacting the isocyanate group of an ethylenically unsaturated monomer having an isocyanate group with the isocyanate group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer.

[0108] Examples of ethylenically unsaturated monomers having hydroxyl groups include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. Also included are polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by adding polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred, and from the viewpoint of sensitivity, it is preferable to use a material having 2 to 6 hydroxyl groups, with glycerol mono(meth)acrylate being even more preferred.

[0109] Examples of ethylenically unsaturated monomers having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0110] Other monomers that can constitute alkali-soluble resins include, in addition to the other ethylenically unsaturated monomers already described, N-substituted maleimides, alkylene oxy group-containing monomers, phosphate ester group-containing ethylenically unsaturated monomers, carboxyl group-containing ethylenically unsaturated monomers, and the like. N-substituted maleimides include, for example, cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-( Examples include 2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzoimidazolyl)phenyl]maleimide, and 9-maleimidacridine. Examples of alkylene oxy group-containing monomers include EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0111] For carboxyl group-containing ethylenically unsaturated monomers, the monomers already described can be used.

[0112] Phosphate ester group-containing ethylenically unsaturated monomers are, for example, compounds obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphate.

[0113] (Alkali-soluble resin without ethylenically unsaturated double bonds) The coloring composition for color filters of the present invention may contain an alkali-soluble resin that does not have an ethylenically unsaturated double bond in order to adjust the degree of hardening of the coating.

[0114] In this invention, the weight-average molecular weight (Mw) of the alkali-soluble resin is 2,000 to 40,000, preferably 3,000 to 30,000, and more preferably 4,000 to 20,000, in order to impart alkali-developable solubility. Furthermore, the Mw / Mn value is preferably 10 or less. If the weight-average molecular weight (Mw) is less than 2,000, adhesion to the substrate decreases, and the exposure pattern becomes difficult to retain. If it exceeds 40,000, alkali-developable solubility decreases, residue is generated, and the linearity of the pattern deteriorates. In this invention, the acid value of the alkali-soluble resin is 50 to 200 (KOH mg / g) to impart alkali-developable solubility, preferably in the range of 70 to 180, and more preferably in the range of 90 to 170. If the acid value is less than 50, alkali-developable solubility decreases, residue is generated, and the linearity of the pattern deteriorates. If it exceeds 200, adhesion to the substrate decreases, and the exposure pattern becomes difficult to retain.

[0115] Each raw material used in the synthesis of the binder resin can be used individually or in combination of two or more types.

[0116] <Thermosetting compounds> In the present invention, a thermosetting compound can be further included in combination with a thermoplastic resin as the binder resin. When producing a color filter using the coloring composition for color filters of the present invention, the inclusion of a thermosetting compound reacts during the firing of the filter segment, increasing the crosslinking density of the coating film. This improves the heat resistance of the filter segment, suppresses pigment aggregation during the firing of the filter segment, and improves the contrast ratio.

[0117] The thermosetting compound may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. Examples of thermosetting compounds include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds, but the present invention is not limited thereto. In the coloring compositions for color filters of the present invention, epoxy compounds and oxetane compounds are preferably used.

[0118] <Method for manufacturing a colored composition for color filters> Any conventionally known method can be used to manufacture the colored composition for color filters. The method is not particularly limited as long as it can finely and uniformly disperse the pigment (A) and the dye derivative (B) in a pigment carrier containing a resin-type dispersant (C) and an organic solvent (D). Among these, bead dispersion, in which minute beads with a diameter of 1 mm to 0.01 mm are introduced into a device such as a sand mill and dispersed, is preferred because the material and particle size of the beads can be arbitrarily changed.

[0119] The dispersion time is preferably 1 to 72 hours, and more preferably 2 to 24 hours. The temperature of the colored composition for the color filter during dispersion is preferably 100°C or lower, and more preferably 40°C or lower. The diameter of the beads is preferably 0.3 mm or lower. The bead material is preferably glass, alumina, steel, stainless steel, zircon, zirconia, etc.

[0120] <<Color-curable composition for color filters>> The colored composition for color filters of the present invention can be used as a colored curable composition for color filters by mixing it with a photopolymerization initiator (E) and a polymerizable compound (F), described later, after it has been coated onto a substrate such as glass and cured by irradiation with light such as ultraviolet light to form a fine pattern.

[0121] <Photopolymerization initiator (E)> The color-curable composition for color filters of the present invention contains a photopolymerization initiator (E). The inclusion of the photopolymerization initiator (E) allows the composition to be cured by ultraviolet irradiation, enabling the formation of filter segments by photolithography. It is preferable to prepare the composition in the form of a solvent-developable or alkali-developable color-curable composition by adding the photopolymerization initiator (E).

[0122] Examples of photopolymerization initiators (E) include 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-[( Acetophenone compounds such as 4-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( Benzophenone compounds such as t-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)-s-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.

[0123] Photopolymerization initiators can be used alone or in combination of two or more types.

[0124] In the present invention, it is preferable that the photopolymerization initiator (E) contains an oxime ester-based photopolymerization initiator.

[0125] (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 as patterns can be formed with less exposure compared to using other photopolymerization initiators.

[0126] As oxime compounds, the compounds described in Japanese Patent Publication No. 2001-233842, the compounds described in Japanese Patent Publication No. 2000-80068, the compounds described in 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.

[0127] Examples of oxime compounds 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 compounds that are colorless or highly transparent and do not easily discolor other components.

[0128] 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.

[0129] [Oxime ester photopolymerization initiators with a diphenyl skeleton] [ka]

[0130] [Oxime ester-based photopolymerization initiators with a carbazole skeleton] [ka]

[0131] [Oxime ester photopolymerization initiators containing a fluorene skeleton] [ka]

[0132] [Photopolymerization initiator having two oxime ester groups] Examples of photopolymerization initiators include those having two oxime ester groups on either side of a carbazole skeleton or a phenothiazine skeleton, as shown below. [ka]

[0133] 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.

[0134] The content of the photopolymerization initiator (E) 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 solid content of the colored curable composition. When an appropriate amount is added, the photocurability and developer resistance are improved and the surface condition is improved.

[0135] <Polymerizable compound (F)> The color-curable composition for color filters of the present invention contains a polymerizable compound (F). The polymerizable compound (F) includes monomers or oligomers that harden upon exposure to ultraviolet light or heat to produce a transparent resin.

[0136] Polymerizable compounds (F) include, 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, and 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.

[0137] (Polymerizable compounds containing acidic groups) Polymerizable compound (F) may contain a photopolymerizable monomer having an acidic group. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups.

[0138] Examples of photopolymerizable monomers 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.

[0139] (Polymerizable compound containing urethane bonds) The polymerizable compound (F) may contain monomers having ethylenically unsaturated bonds and urethane bonds. Examples of such monomers include polyfunctional urethane acrylates obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing (meth)acrylate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting that with a hydroxyl group-containing (meth)acrylate.

[0140] 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.

[0141] Furthermore, polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanates.

[0142] Polymerizable compound (F) can be used alone or in combination of two or more types.

[0143] The amount of polymerizable compound (F) is preferably 1 to 50% by mass, and more preferably 2 to 40 parts by mass, based on 100% by mass of the solid content of the colored curable composition. Adding an appropriate amount further improves curability and developability.

[0144] <Sensitizer> Furthermore, the colored curable composition for color filters 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.

[0145] 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.

[0146] 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.

[0147] Sensitizers can be used alone or in combination of two or more types.

[0148] 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 (E). Including an appropriate amount further improves curability and developability.

[0149] <Thiol-based chain transfer agents> The color curable composition for color filters of the present invention preferably contains a thiol-based chain transfer agent. By using thiols together with a photopolymerization initiator, 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 color curable composition for color filters.

[0150] 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.

[0151] Examples of polyfunctional thiols include hexanedithiol and decanedithiol. Examples include 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol 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, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate are used.

[0152] Thiol-based chain transfer agents can be used alone or in combination of two or more types.

[0153] The content of the thiol-based chain transfer agent is preferably 0.1 to 10% by mass, and more preferably 0.1 to 3% by mass, based on 100% by mass of the solid content of the colored curable 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.

[0154] <Polymerization inhibitor> The color-curable composition for color filters 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.

[0155] 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.

[0156] The polymerization inhibitor content is preferably 0.01 to 0.4 parts by mass per 100% by mass of the solid content of the colored curable 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.

[0157] <UV absorber> The color-curable composition for color filters of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorption function, and examples include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, and salicylate compounds.

[0158] The UV absorber content is preferably 5 to 70% by mass of the total 100% by mass of the photopolymerization initiator (E) and UV absorber. Including an appropriate amount further improves resolution after development.

[0159] Furthermore, the total content of the photopolymerization initiator (E) and the ultraviolet absorber is preferably 1 to 20% by mass of the solid content of the colored curable composition. Including an appropriate amount further improves the adhesion between the substrate and the coating, resulting in good resolution.

[0160] 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.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] <Antioxidant> The color-curable composition for color filters of the present invention may contain an antioxidant. The antioxidant prevents the photopolymerization initiator (E) and thermosetting compounds contained in the color-curable composition from oxidizing and yellowing due to the heat process during thermal curing and ITO annealing, thereby improving the transmittance of the coating film. In particular, when the colorant concentration of the color-curable composition is high, the amount of coating film crosslinking components decreases, so countermeasures such as using highly sensitive crosslinking components or increasing the amount of photopolymerization initiator (E) are taken, which can lead to a phenomenon where yellowing during the heat 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.

[0165] 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.

[0166] 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.

[0167] Antioxidants can be used alone or in combination of two or more types.

[0168] Furthermore, an antioxidant content of 0.5 to 5.0% by mass per 100% by mass of the solid content of the colored curable composition is more preferable because it results in good transmittance, spectral characteristics, and sensitivity.

[0169] <Leveling agent> In the color-curable composition for color filters of the present invention, it is preferable to add a leveling agent 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 leveling agents.

[0170] 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.

[0171] 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.

[0172] Examples of fluorine-based surfactants include surfactants or leveling agents having fluorocarbon chains.

[0173] 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.

[0174] 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.

[0175] 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.

[0176] Cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

[0177] More specifically, examples include Acetamine 24, Cotamin 24P, 60W, and 86P Concentrate manufactured by Kao Corporation.

[0178] 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.

[0179] 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.

[0180] 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.

[0181] More specifically, examples include Anchitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0182] When the color-curable composition for color filters of the present invention contains a surfactant, the amount of surfactant 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 composition of the present invention. Within this range, a good balance is achieved between the coatability, pattern adhesion, and transmittance of the color-curable composition. The color-curable composition for color filters of the present invention may contain only one type of surfactant, or it may contain two or more types. If it contains two or more types, it is preferable that the total amount thereof is within the above range.

[0183] <Storage stabilizer> The colored curable composition for color filters 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 the colorant (100% by mass).

[0184] <Adhesion enhancer> The color-curable composition for color filters 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.

[0185] 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 colorant in the colored curable composition. Within this range, the effect is greater, and the balance between adhesion, resolution, and sensitivity is good, making it more preferable.

[0186] <Removal of coarse particles> The colored composition and color-curable composition for color filters of the present invention are 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 colored composition substantially contains no particles of 0.5 μm or larger. More preferably, the particles are 0.3 μm or smaller.

[0187] <Metal Removal> If specific metal elements are present in large quantities as impurities other than the components of the pigment (A) and dye derivative (B) in the colored composition and the colored curable composition, it can impair the dispersion stability over time, and may also lead to a decrease in heat resistance or sensitivity. Furthermore, color filters made using this may have foreign matter generated, which can easily result in a decrease in brightness. Preferably, the total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) in the colored composition and colored curable composition for color filters of the present invention is 500 ppm by mass or less.

[0188] The total amount of specific metal elements contained in the colored composition and the colored curable composition is more preferably 300 ppm by mass or less, and particularly preferably 200 ppm by mass or less. The lower limit of the total amount of specific metal elements is not particularly limited, but is preferably 1 ppm by mass or more, and more preferably 5 ppm by mass or more. Within the above range, it is possible to obtain a colored composition and a colored curable composition that can form a color filter with reduced costs, excellent storage stability, and minimal generation of foreign matter and reduction in brightness.

[0189] The amount of each specific metal element contained in the colored composition and the colored curable composition is preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less.

[0190] Furthermore, it is preferable that the metals constituting the pigment (A) and dye derivative (B), such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co, contain as few impurities as possible that do not function effectively, and these can be removed in the same way as specific metal elements by the following method. In addition, it is preferable that the concentrations of Mn, Cs, Ti, Co, Si, Pd, etc., that have been introduced due to materials used in the manufacturing process of the various raw materials of the colored curable composition (for example, catalysts) be low.

[0191] Methods for removing colorants (A) or metals introduced from equipment during the manufacturing process include washing with water as described in Japanese Patent Publication No. 2010-83997, Japanese Patent Publication No. 2018-36521, Japanese Patent Publication No. Hei 7-198928, Japanese Patent Publication No. Hei 8-333521, Japanese Patent Publication No. 2009-7432, etc., and methods for removing magnetic foreign matter using a magnet as described in Japanese Patent Publication No. 2011-48736, and one or more of these methods may be used as appropriate.

[0192] The content of specific metal elements can be measured by inductively coupled plasma atomic emission spectroscopy (ICP).

[0193] <Color Filter> The color filter of the present invention comprises a filter segment formed from the coloring composition for color filters or the color curable composition for color filters 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.

[0194] The color filter of the present invention will be described in detail through its manufacturing method.

[0195] A method for forming filter segments in the color filter of the present invention includes, for example, the steps of: applying the color-curable composition for color filters of the present invention onto a support to form a color-curable composition layer; exposing the color-curable composition layer in a patterned manner; and developing and removing the unexposed areas to form a colored pattern. Furthermore, the present invention provides a method comprising the steps of: applying the color-curable composition for color filters of the present invention onto a support to form a color-curable composition layer and curing it to form a color layer; forming a photoresist layer on the color layer; patterning the photoresist layer by exposure and development to obtain a resist pattern; and dry etching the color layer using the resist pattern as an etching mask to form a color pattern. In other words, the color filter of the present invention can be formed by photolithography or by dry etching.

[0196] In the present invention, the support for forming the filter segment can be, for example, a substrate made of a material such as glass, resin, or silicon. An organic light-emitting layer may be formed on these substrates. An image sensor such as a CCD or CMOS may also be formed on the substrate. Furthermore, an undercoat layer may be provided on the substrate as needed to improve adhesion with the upper layer, prevent diffusion of materials, and flatten the substrate surface, and the support is not particularly limited as long as it can be applied to the formation of the filter segment.

[0197] (Step of forming a colored, curable composition layer) In the step of forming a colored curable composition layer, the colored curable composition for color filters of the present invention is applied to a support to form a colored curable composition layer.

[0198] Various coating methods can be applied to the support of the composition of the present invention, such as dropping, slit coating, spraying, inkjet, rotary coating, casting, roll coating, flexographic printing, screen printing, gravure printing, and offset printing.

[0199] The thickness of the coating film can be appropriately adjusted according to the purpose. The thickness of the film is preferably 0.05 to 20.0 μm, more preferably 0.3 to 10.0 μm.

[0200] (When forming a filter segment by photolithography) When forming a filter segment by photolithography, after drying (pre-baking) the layer formed by coating the composition of the present invention on a substrate as necessary, it is exposed in a pattern through a mask (exposure step), and the unexposed portion is removed by alkali development (development step), and then the pattern is heat-treated (post-baking step) as necessary. [Exposure step] In the exposure step, the layer formed by coating is exposed to a specific pattern through a mask using an exposure apparatus such as a stepper. Thereby, 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 having a wavelength of 300 nm or less can be used. Examples of the light having a wavelength of 300 nm or less include KrF line (wavelength 248 nm), ArF (wavelength 193 nm), and the like. In addition, at the time of exposure, the light may be continuously irradiated for exposure, or the light irradiation and pause may be repeated in a short time (for example, at the millisecond level or less) cycle for exposure (pulse exposure).

[0201] [Development step] Next, by performing alkali development treatment, the layer of the unexposed portion is eluted in an alkaline aqueous 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, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, roughness and peeling of the pattern are suppressed, and the residual film rate after development is improved. Examples of the development method include dip method, spray method, paddle method, etc. The development temperature is preferably 15 to 40 °C. After alkaline development, it is preferable to wash with pure water.

[0202] [Post-baking step] After development, heat treatment (post-baking) can be performed if necessary. The resistance of the film is improved by post-baking. The temperature is preferably 80 to 300 °C. Also, the time is preferably about 2 minutes to 1 hour. When a material with low heat resistance is used for the substrate or when an organic electroluminescence element is used as the light source, etc., the temperature is preferably 150 °C or lower, more preferably 130 °C or lower.

[0203] (When forming the filter segment by dry etching method) When forming the filter segment by dry etching method, for example, a layer formed by coating the composition of the present invention on a substrate is heated and cured. Next, after forming a patterned photoresist layer on the cured film, dry etching is performed on the cured film using an etching gas with the patterned photoresist layer as a mask. Regarding the pattern formation by dry etching method, the method described in JP-A-2013-064993 can be referred to.

[0204] [Solid-state imaging device] The solid-state imaging device of the present invention includes the color filter of the present invention. The form used for the solid-state image sensor is not particularly limited, but for example, it may have a substrate on which a plurality of photodiodes constituting the light-receiving area of ​​the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) and transfer electrodes made of polysilicon or the like are provided, a light-shielding film with an opening only for the light-receiving portion of the photodiode is provided on the photodiode and transfer electrodes, a device protection film made of silicon nitride or the like is provided on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and a filter on the device protection film. Furthermore, it may have a configuration in which a light-gathering means (e.g., a microlens; the same applies hereinafter) is provided on the device protection film below the filter (closer to the substrate), or a configuration in which the light-gathering means is provided on the filter. In addition, the filter may have a structure in which a hardened film forming each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partition walls. In this case, it is preferable that the partition walls have a low refractive index with respect to each colored pixel. The imaging device equipped with the solid-state image sensor of the present invention can be used in a variety of applications, such as digital cameras, electronic devices with imaging functions (smartphones, tablet terminals, etc.), in-vehicle cameras, surveillance cameras, and optical sensors.

[0205] <Image display device> The image display device of the present invention comprises the color filter of the present invention. Examples of image display devices include liquid crystal displays and organic EL displays. The form used for an image display device is not particularly limited, as long as it functions as an image display device. For example, the configurations described in "Next-Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994) are examples. For definitions of image display devices and details of various image display devices, see, for example, "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Junsho Ibuki, Sangyo Tosho Co., Ltd., published in 1989). [Examples]

[0206] The present invention will be described in detail below with reference to examples, but the present invention is not limited to the following examples unless it exceeds the spirit of the invention. Unless otherwise specified, "parts" refers to mass and "%" refers to mass percent. The solid content of the resin component is the value obtained by measuring the loss of drying when 0.5 g of the resin solution is accurately weighed and placed in a 180°C dryer for 20 minutes.

[0207] Prior to the examples, we will explain the calculation methods for determining the average molecular weight of the resin, the acid value of the resin, and the amine value of the basic resin-type dispersant.

[0208] (Average molecular weight of resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the resin were measured using gel permeation chromatography (GPC) equipped with a radioisotope detector. An HLC-8220GPC (manufactured by Tosoh Corporation) was used, with two separation columns connected in series. Both columns were packed with two TSK-GEL SUPER HZM-N columns. 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 1 wt% solution of the above eluent and injected in 20 microliters. All molecular weights are polystyrene equivalents.

[0209] (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 (mgKOH / g) of the resin solution. 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.

[0210] (Amine value (mgKOH / g) of basic resin-type dispersants) The amine value of basic resin-type dispersants is calculated by converting the total amine value (mgKOH / g), measured according to the ASTM D 2074 method, into a solid content equivalent.

[0211] <Manufacturing of dye derivative (B1)> [Production Example 1-1] Production of Pigment Derivative (B1-1) 84 g of 8-aminoquinazoline was dissolved in 1100 g of methanol with stirring. Subsequently, 57 g of sodium carbonate and 112 g of 4-acetamidobenzenesulfonyl chloride were added. The mixture was stirred at 25°C to 35°C for 4 hours. After stirring, 600 g of water and 152 g of 35%-hydrochloric acid were added, and the mixture was heated to the reflux temperature, and methanol was distilled off until the reflux temperature reached 100°C. After distillation, 400 g of water was added, and after cooling to 60°C or lower, the pH was adjusted to 12.0 with a 25%-aqueous sodium hydroxide solution, and the mixture was stirred at 50°C for 1 hour. After leaving it to stand at room temperature, the pH was adjusted to 4.0 with acetic acid, and the mixture was stirred at room temperature for 1 hour. Filtration, washing with water, and drying gave 116 g of Intermediate 1 represented by Formula 101.

[0212] Formula 101 [Chemical Formula]

[0213] 45 g of cyanuric chloride was added to 400 g of acetone cooled to 5°C and dissolved. A solution in which Intermediate 1 represented by Formula 101 was dissolved in 120 g of N-methyl-2-pyrrolidone was added dropwise while maintaining 5°C. Subsequently, 85 g of a 10%-aqueous sodium carbonate solution was added dropwise while maintaining 5°C as well, and the product was filtered and washed with water. The obtained water cake was slurried again in 400 g of acetone, filtered, and washed with acetone to obtain Intermediate 2 (acetone-containing cake) represented by Formula 102.

[0214] Formula 102 [Chemical Formula]

[0215] )]] The intermediate 2 (acetone-containing cake) represented by formula 102 was gradually added to a mixed solution of 320 g of 1,4-dioxane and 105 g of diethylaminopropylamine at a temperature below 60°C. The mixture was then stirred at 50-60°C for 1.5 hours and then at 90°C for 3.5 hours. 200 g of water was added to the reaction mixture, and the mixture was heated to reflux temperature to remove the 1,4-dioxane by distillation. The mixture was cooled to room temperature, and the pH was adjusted to 4.0 with acetic acid to dissolve the product. The reaction mixture was poured into 1 L of water, and the pH was adjusted to 11 with sodium hydroxide. The supernatant was removed by decantation and washed until neutral. The mixture was vacuum-dried at 50°C to obtain 96 g of intermediate 3 represented by formula 103.

[0216] formula 103 [ka]

[0217] 270 g of benzoic acid was melted at 160°C, and intermediate 3, represented by formula 103, was added and dissolved. Next, 103 g of tetrachlorophthalic anhydride was added, and the mixture was stirred at 160°C for 4 hours. After stirring, 1000 g of methanol was gradually added. The reaction mixture was poured into 7500 g of water, the pH was adjusted to 11 with aqueous sodium hydroxide solution, and the mixture was stirred at 80°C for 1 hour. The resulting precipitate was filtered, washed with water, and dried to obtain 98 g of the dye derivative (B1-1) represented by formula 104. The molecular weight of the obtained dye derivative (B1-1) was measured using a Bruker MALDI TOF-MS autoflex speed, and a peak corresponding to the molecular weight of the dye derivative (B1-1) was confirmed.

[0218] formula 104 [ka]

[0219] [Manufacturing Examples 1-2 to 1-7, 1-9, 1-10] Production of dye derivatives (B1-2~1-7, 1-9, 1-10) Dye derivatives (B1-2 to 1-7, 1-9, and 1-10) were obtained in the same manner as for dye derivative (B1-1), except that the raw materials used in the production of dye derivative (B1-1)—8-aminoquinaldine (general formula (201)), 4-acetamidobenzenesulfonyl chloride (general formula (202)), tetrachlorophthalic anhydride (general formula (203)), and diethylaminopropylamine (general formula (204))—were replaced with those listed in Tables 1-1 to 1-4. The structures of the produced dye derivatives are shown in Table 1-5.

[0220] [Manufacturing Examples 1-8] Production of dye derivatives (B1-8) Dye derivative (B1-8) was obtained in the same manner as for dye derivative (B1-1), except that the amount of diethylaminopropylamine used in the production of dye derivative (B1-1) was changed to 55 g. The molecular weight of the obtained dye derivative (B1-8) was measured using a Bruker MALDI TOF-MS autoflex speed time-of-flight mass spectrometer, and a peak corresponding to the molecular weight of the dye derivative (B1-8) was confirmed. It is thought that by changing the amount of diethylaminopropylamine added, the amine was hydrolyzed without being sufficiently substituted, resulting in a structure containing a hydroxyl group.

[0221] General formula (201) [ka]

[0222] [Table 1-1]

[0223] General formula (202) [ka]

[0224] [Table 1-2]

[0225] General formula (203) [ka]

[0226] [Table 1-3]

[0227] General formula (204) [ka]

[0228] [Table 1-4] Manufacturing Example 1-9: Prepared by replacing diethylaminopropylamine with 1-piperidineethanol.

[0229] [Table 1-5]

[0230] <Manufacturing of dye derivative (B2)> [Manufacturing Example 2-1] Production of dye derivative (B2-1) Intermediate 2 (acetone-containing cake) represented by formula 102, obtained by the same method as in Production Example 1-1, was gradually added at a temperature below 60°C to a mixed solution of 320 g of 1,4-dioxane and 105 g of diethylaminopropylamine. The mixture was then stirred at 50-60°C for 1.5 hours and then at 90°C for 3.5 hours. 200 g of water was added to the reaction mixture, and the mixture was heated to reflux temperature to remove the 1,4-dioxane by distillation. The mixture was cooled to room temperature, and the pH was adjusted to 4.0 with acetic acid to dissolve the product. The reaction mixture was poured into 1 L of water, the pH was adjusted to 11 with sodium hydroxide, and then the mixture was stirred at 80°C for 1 hour. The resulting precipitate was filtered, washed with water, and dried to obtain the dye derivative (B2-1) represented by formula 105. The molecular weight of the obtained dye derivative (B2-1) was measured using a Bruker MALDI TOF-MS autoflex speed time-of-flight mass spectrometer, and a peak corresponding to the molecular weight of the dye derivative (B2-1) was confirmed.

[0231] formula 105 [ka]

[0232] [Manufacturing Examples 2-2 to 2-7, 2-9, 2-10] Production of dye derivatives (B2-2~2-7, 2-9, 2-10) Dye derivatives (B2-2 to 2-7, 2-9, 2-10) were obtained in the same manner as dye derivative (B2-1), except that the raw materials used in the production of dye derivative (B2-1) were changed to the raw materials listed in Tables 1-1, 1-2, and 1-4 used in the production of the corresponding branch number dye derivative (B1). The structures of the produced dye derivatives are shown in Table 2. (For example, the dye derivative (B2-2) was produced using the same raw materials as those used in the production of dye derivative (B1-2), and the dye derivative (B2-3) was produced using the same raw materials as those used in the production of dye derivative (B1-3).)

[0233] [Manufacturing Example 2-8] Production of dye derivative (B2-8) Dye derivative (B2-8) was obtained using the same method as for dye derivative (B2-1), except that the amount of diethylaminopropylamine used was changed to 55 g. The molecular weight of the obtained dye derivative (B2-8) was measured using a Bruker MALDI TOF-MS autoflex speed time-of-flight mass spectrometer, and a peak corresponding to the molecular weight of the dye derivative (B2-8) was confirmed. It is thought that by changing the amount of diethylaminopropylamine added, the amine was hydrolyzed without being sufficiently substituted, resulting in a structure containing a hydroxyl group.

[0234] [Table 2]

[0235] <Manufacturing of dye derivative (B3)> [Manufacturing Example 3-1] Production of dye derivative (B3-1) Intermediate 3, represented by formula 103 and obtained by the same method as in Production Example 1-1, was added to 270 g of benzoic acid molten at 160°C and dissolved. Next, 103 g of tetrachlorophthalic anhydride was added and the mixture was stirred at 160°C for 4 hours. After stirring, 1000 g of methanol was gradually added. The reaction mixture was poured into 7500 g of water, the pH was adjusted to 11 with an aqueous sodium hydroxide solution, and the mixture was stirred at 80°C for 5 hours. The resulting precipitate was filtered, washed with water, and dried to obtain the dye derivative (B3-1) represented by formula 106. The molecular weight of the obtained dye derivative (B3-1) was measured using a Bruker MALDI TOF-MS autoflex speed time-of-flight mass spectrometer, and a peak corresponding to the molecular weight of the dye derivative (B3-1) was confirmed.

[0236] formula 104 [ka]

[0237] [Manufacturing Examples 3-2 to 3-7, 3-9, 3-10] Production of dye derivatives (B3-2~3-7, 3-9, 3-10) Dye derivatives (B3-2~3-7, 3-9, 3-10) were obtained in the same manner as dye derivative (B3-1), except that the raw materials used in the production of dye derivative (B3-1) were changed to the raw materials listed in Tables 1-1, 1-2, and 1-4 used in the production of the corresponding branch number dye derivative (B1). The structures of the produced dye derivatives are shown in Table 3. (For example, dye derivative (B3-2) was produced using the same raw materials as dye derivative (B1-2), and dye derivative (B3-3) was produced using the same raw materials as dye derivative (B1-3).)

[0238] [Manufacturing Example 3-8] Production of dye derivatives (B3-8) Dye derivative (B3-8) was obtained in the same manner as for dye derivative (B3-1), except that the amount of diethylaminopropylamine used in the production of dye derivative (B3-1) was changed to 55 g. The molecular weight of the obtained dye derivative (B3-8) was measured using a Bruker MALDI TOF-MS autoflex speed time-of-flight mass spectrometer, and a peak corresponding to the molecular weight of the dye derivative (B3-8) was confirmed. It is thought that by changing the amount of diethylaminopropylamine added, the amine was hydrolyzed without being sufficiently substituted, resulting in a structure containing a hydroxyl group.

[0239] [Table 3]

[0240] <Manufacturing of dye derivative (B)> [Manufacturing Examples 4-1 to 4-22] Manufacturing of dye derivatives (B-1 to B-22) The dye derivatives prepared were mixed in the proportions shown in Table 4 to obtain dye derivatives (B-1) to (B-22).

[0241] [Table 4]

[0242] <Manufacturing of micronized pigments> [Manufacturing Example A1] Production of finely milled pigments by solvent-salt milling method Manufacturing of micronized pigments (A-1) 100 parts of commercially available CI Pigment Red 254 (PR254) (BASF's "Irgazine Red D3656 HD"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 6 hours, followed by salt milling. The resulting mixture was added to 3 liters of warm water and stirred for 1 hour while heating to 70°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 obtain 98 parts of finely ground pigment (A-1).

[0243] [Manufacturing examples A2~10] Manufacturing of micronized pigments (A-2~10) Micronized pigments (A-2 to A-10) were manufactured using the same method as micronized pigment (A-1), except that the pigments were changed as shown in Table 5.

[0244] [Manufacturing example P11] Manufacturing of micronized pigments (A-11) 90 parts of commercially available CI Pigment Red 254 (PR254) (BASF's "Irgazine Red D3656 HD"), 10 parts of pigment derivative (B-1), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 6 hours, followed by salt milling. The resulting mixture was added to 3 liters of warm water and stirred for 1 hour while heating to 70°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 obtain 95 parts of pigment (A-11).

[0245] [Manufacturing example A12] Production of finely milled pigments by acid paste method Manufacturing of micronized pigment (A-12) 80 parts of commercially available CI Pigment Red 254 (PR254) (BASF's "Irgazine Red D3656 HD"), 10 parts of pigment derivative (B-1), and 1000 parts of 98% sulfuric acid aqueous solution were mixed and stirred at 40°C for 150 minutes. This solution was added to 10000 parts of 5°C water with stirring. The precipitate was filtered, washed with water until neutral, and dried to obtain 91 parts of finely ground pigment (A-12).

[0246] Details of the micronized pigments (A-1 to A-12) are shown in Table 5.

[0247] [Table 5] CI Pigment Red 177: CINIC's "Cinilex Red SR3C" CI Pigment Red 179: Clariant "Hostaperm Red P2GL-WD" CI Pigment Red 269: Hangzhou Epsilon Chemical Co., Ltd. "Naphthol Red RA" CI Pigment Yellow 138: Hangzhou Epsilon Chemical Co., Ltd. "Quinophthalone Yellow HD-T" CI Pigment Yellow 139: Clariant "Graphtol Yellow H2R" CI Pigment Yellow 150: Clariant "Hostaperm Yellow HN4G" CI Pigment Green 36: Toyo Color Co., Ltd. "Lionol Green 6YK" CI Pigment Green 58: DIC Corporation "Fastogen Green A110" CI Pigment Green 59

[0248] <Manufacturing of resin-type dispersant (C)> [Manufacturing example C1] Preparation of resin-type dispersant (C-1) solution 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 reaction vessel was heated to 50°C and stirred, and 12 parts 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and the mixture was reacted for 7 hours while adding a solution of 0.1 parts 2,2'-azobisisobutyronitrile added to 90 parts propylene glycol monomethyl ether acetate. Solid content measurement confirmed that 95% had reacted. 19 parts pyromellitic anhydride, 100 parts propylene glycol monomethyl ether acetate, and 0.4 parts 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 undergone half-esterification by measuring the acid value, the reaction was terminated. Propylene glycol monomethyl ether acetate was added to dilute the solution to a solid content of 40% by measuring the solid content, and a solution of a resin-type dispersant (C-1) having aromatic carboxyl groups with an acid value of 77 mg KOH / g and a weight-average molecular weight (Mw) of 8,500 was obtained.

[0249] [Manufacturing example C2~5] Preparation of resin-type dispersant (C-2~C-5) solutions The resin-type dispersants (C-2 to C-5) were manufactured in the same manner as the resin-type dispersant (C-1) solution, except that the raw materials and preparation amounts listed in Table 6 were used.

[0250] [Table 6]

[0251] [Manufacturing example C6] Preparation of resin-type dispersant (C-6) solution In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic dianhydride, 23.5 parts of cyclohexanone, and 0.01 parts of mono-n-butyltin(IV) oxide were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 100°C and the mixture was reacted for 7 hours. After confirming that more than 97% of the acid anhydrides had been half-esterified by measuring the acid value, the temperature in the system was cooled to 70°C, and 80 parts of methyl methacrylate and 20 parts of hydroxyethyl methacrylate were charged. A solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 26.2 parts of cyclohexanone was added, and the mixture was reacted for 10 hours. The reaction was terminated after confirming that 95% of polymerization had progressed by measuring the solid content. After the reaction was complete, the solid content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a solution of resin-type dispersant (C-6) with a weight-average molecular weight (Mw) of 9500.

[0252] [Manufacturing example C7] Preparation of resin-type dispersant (C-7) solution In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 80 parts n-butyl acrylate, 60 parts methyl methacrylate, 20 parts methacrylic acid, 20 parts Karenz MOI-BM (Showa Denko), 20 parts ETERNACOLLOXMA (Ube Industries), and 100 parts propylene glycol monomethyl ether acetate were charged and the mixture was purged with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 14 parts 2-mercapto-2-methyl-1,3-propanediol with 0.1 parts 2,2'-azobisisobutyronitrile was added, and the mixture was reacted for 10 hours. Solid content measurement confirmed that 95% of the mixture had reacted. Next, 39 parts of BPAF:9,9-bis(3,4-dicarboxyphenyl)fluorendiohydride (manufactured by JFE Chemical Corporation), 106 parts of C-1015N (bifunctional polycarbonate polyol, trade name Kuraray Polyol C-1015N (hydroxyl value 112 mg KOH / g, manufactured by Kuraray Co., Ltd.)), 33 parts of trimellitic anhydride, 392 parts of cyclohexanone, and 0.40 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. The reaction was terminated after confirming that more than 98% of the acid anhydrides had been half-esterified by measuring the acid value. The solids content was adjusted to 40% with propylene glycol monomethyl ether acetate to obtain a solution of resin-type dispersant (C-7) with an acid value of 94 mg KOH / g and a weight-average molecular weight (Mw) of 7000.

[0253] <Manufacturing of binder resin> [Manufacturing example BIN1] Synthesis of alkali-soluble resin solution (1) 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 32.7 parts dicyclopentanyl methacrylate, 25.7 parts benzyl methacrylate, 41.5 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 20 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 21.1 parts of acrylic acid (100% of the glycidyl groups produced in this reaction), 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 content acid value reached 0.5, at which point the reaction was terminated to obtain an acrylic resin solution. Subsequently, 37.3 parts of tetrahydrophthalic anhydride (84% of the hydroxyl groups produced in this reaction) and 0.5 parts of triethylamine were added and the mixture was reacted at 120°C for 3.5 hours to obtain an acrylic 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 solids content. Propylene glycol monomethyl ether acetate was added to the previously synthesized resin solution so that the solids content was 40% by mass to obtain an alkali-soluble resin solution (1) with a mass-average molecular weight (Mw) of 18000.

[0254] <Manufacturing of colored compositions for color filters> [Manufacturing example MB1] Preparation of a colored composition (MB-1) for color filters CI Pigment Red 177: 12.0 parts of CINIC's "Cinilex Red SR3C", 15.0 parts of resin-type dispersant (C-1) solution, 5.0 parts of alkali-soluble resin solution (1), and 68.0 parts of propylene glycol monomethyl ether acetate were uniformly stirred and mixed. Then, using 0.5 mm diameter zirconia beads, the mixture was dispersed for 3 hours in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII"), and filtered through a 1 μm pore size filter to obtain a colored composition for color filters (MB-1).

[0255] [Example 1] Preparation of a colored composition (M-1) for color filters After uniformly stirring and mixing 11.0 parts of micronized pigment (A-1), 1 part of dye derivative (B-1), 15.0 parts of resin-type dispersant (C-1) solution, 5.0 parts of alkali-soluble resin solution (1), and 68.0 parts of propylene glycol monomethyl ether acetate, the mixture was dispersed for 3 hours using 0.5 mm diameter zirconia beads in an Eiger mill (Eiger Japan "Mini Model M-250 MKII"), and then filtered through a 1 μm pore size filter to obtain a colored composition for color filters (M-1).

[0256] [Examples 2-47, Comparative Examples 1-13] Preparation of colored compositions (M-2 to 60) for color filters Color filter coloring compositions (M-2 to M-60) were prepared in the same manner as color filter coloring composition (M-1), except that the composition was changed as shown in Table 7. If the solid content of the resin-type dispersant differed, the amount of organic solvent was appropriately adjusted so that the solid content of the resin-type dispersant used during dispersion was equivalent to that of Example 1.

[0257] <Evaluation of colored compositions for color filters> The obtained colored compositions for color filters were evaluated using the method described below. The evaluation results are shown in Table 7.

[0258] (Evaluation of contrast ratio (CR)) Using a spin coater, each prepared color filter coloring composition was applied to a glass substrate, dried at 60°C for 5 minutes, and then heated at 230°C for 20 minutes to form a coating film. During this process, the spin coater speed was varied to form three coating films with a thickness of approximately 1.5 μm. A surface shape analyzer DEKTAK150 (ULVAC ES Corporation) was used to measure the film thickness. For each obtained coating film, the brightness and darkness were measured using a contrast tester (CT-1BF, Tsubosaka Electric Co., Ltd.), and the contrast ratio (brightness / darkness) was determined from these values. The film thickness and contrast ratio were then plotted on a graph, and an approximate straight line was drawn to read the contrast ratio at a film thickness of 1.5 μm.

[0259] (Membrane defect evaluation) Each color filter coloring composition was placed in a sealed container and subjected to a temperature cycling test at 5°C for 4 hours and 25°C for 2 hours for 150 days. After that, the coloring composition was removed from the sealed container and applied to a glass substrate using a spin coater to a dry film thickness of 0.5 μm. The coating film for evaluation was then heated on a 100°C hot plate for 180 seconds (pre-bake). The coating film on the glass substrate was observed visually using an optical microscope, with 10 fields of view of a 0.5 mm square area magnified 100 times. The number of defects on the film surface was counted, and the defects were evaluated according to the following criteria. ◎: No defects were found within the scope of evaluation. ○: Number of defects: 1-5 ×: More than 6 defects

[0260] [Table 7] BYK-110: Disperbyk-110 manufactured by Big Chemie (52% solids content) BYK-6919: Disperbyk-6919 manufactured by Big Chemie (60% solids content) PGMAc: Propylene glycol monomethyl ether acetate Metobuta:3-Methoxybutanol Anon: Cyclohexanone

[0261] As shown in Table 7, the colored composition for color filters of the present invention resulted in a good contrast ratio and few film defects.

[0262] <Manufacturing of colored curable compositions for color filters> [Example 101] Preparation of a colored curable composition (R-1) for color filters The following raw materials were mixed and stirred, and filtered through a 1.0 μm pore size filter to obtain a colored curable composition (R-1) for color filters. Coloring composition for color filters (M-1) 24.0 parts Coloring composition for color filters (MB-1) 12.0 parts Alkali-soluble resin solution (1) 8.0 parts Polymerizable compound (M-402) 3.8 parts Photopolymerization initiator (compound represented by formula (301)) 0.8 parts Leveling agent (BYK-330 solution) 1.8 parts PGMAc 49.6 parts

[0263] • M-402: Arronix M-402, Dipentaerythritol Pentaacrylate / Dipentaerythritol Hexaacrylate (manufactured by Toagosei Chemical Co., Ltd.) • Photopolymerization initiator (compound represented by formula (301)) Formula (301) [ka] • BYK-330 solution: 1% PGMAc solution of BYK-330 (manufactured by BYK Chemie) • PGMAc: Propylene glycol monomethyl ether acetate

[0264] [Examples 102-138, Comparative Examples 101-104] Preparation of colored curable compositions (R-2) to (R-38) and (R-48) to (R-51) for color filters. Color-curable color-filter compositions (R-2) to (R-38) and (R-48) to (R-51) were obtained in the same manner as in Example 101, except that the types of color-filter coloring compositions were changed as shown in Table 8.

[0265] <Evaluation of colored curable compositions for color filters> The obtained colored curable compositions for color filters were evaluated using the method described below. The evaluation results are shown in Table 8.

[0266] (Evaluation of filtration performance) 30 g of the obtained colored curable composition for color filters was passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number: 39115221) under nitrogen pressure (0.3 MPa), and the amount obtained through the filter was measured and evaluated according to the following criteria. The evaluation criteria are as follows, with a score of 2 or higher being considered usable. 5: Filtration volume of 19.0g or more 4: Filtration volume between 14.0g and 19.0g 3: Filtration volume between 9.0g and 14.0g 2: Filtration amount between 4.0g and 9.0g 1: Filtration amount less than 4.0g

[0267] (Long-term storage evaluation (PCD evaluation)) Each color-curable composition for color filters was applied to a glass substrate by spin coating to a film thickness of 0.6 μm, and then heated on a hot plate at 100°C for 2 minutes to obtain a color-curable composition layer. After the formation of the color-curable composition layer, the post-coating delay (PCD) before exposure was set to either 0 hours or 24 hours. Substrates left for 0 or 24 hours were exposed to ultraviolet light using an ultra-high pressure mercury lamp with an integrated light intensity of 50 mJ / cm2 and an illuminance of 30 mW / cm2, through a mask, to create a 1.4 μm square checkerboard pattern. Subsequently, a 0.2 wt% sodium carbonate aqueous solution was used as the developer, and development was continued for another 15 seconds after the unexposed areas of the coating were gone to form the pattern. The substrate was then rinsed with a spin shower and further washed with pure water to obtain the pattern. For the patterns obtained at PCD0 hours and PCD24 hours, the line width of one pixel in the pattern was measured at 10 arbitrary points within the glass substrate, and the average value was calculated. The line width of the patterns was observed using an electron microscope. Then, the difference between the average line widths of each pattern was calculated. ◎: The difference in line width between each pattern is within ±0.06 μm. ○: The difference in line width between each pattern is greater than ±0.06 μm and within ±0.15 μm. ×: The difference in line width between each pattern exceeds ±0.15 μm.

[0268] [Table 8]

[0269] As shown in Table 8, the colored curable composition for color filters of the present invention showed good filterability and PCD dependence.

[0270] <Preparation of a green-colored, curable composition> Ten parts of DIC's FASTOGEN GREEN A110 (CIPigment Green 58), two parts of BASF's PALIOTOL YELLOWD 0960 (CIPigment Yellow 138), eight parts of BASF's EFKA4300 (as solid content), and 80.0 parts of propylene glycol monomethyl ether acetate were uniformly stirred and mixed. The mixture was then dispersed for 3 hours using 0.5 mm diameter zirconia beads in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII"), and finally filtered through a 5 μm pore size filter to obtain a green colored composition. The obtained green colored composition was mixed with the following raw materials, stirred, and filtered through a 1.0 μm pore size filter to obtain a green colored curable composition. Green coloring composition 36.0 parts Alkali-soluble resin solution (1) 8.0 parts Polymerizable compound (M-402) 3.8 parts Photopolymerization initiator (compound represented by formula (301)) 0.8 parts Leveling agent (BYK-330 solution) 1.8 parts PGMAc 49.6 parts

[0271] <Preparation of a blue-colored, curable composition> Eleven parts of LIONOL BLUE ES (CIPigment BLUE 15:6) manufactured by Toyo Color Co., Ltd., one part of LIONOGENVIOLET FG-6140 (CIPigment Violet 23) manufactured by Toyo Color Co., Ltd., eight parts of EFKA4300 manufactured by BASF as solid content, and 80.0 parts of propylene glycol monomethyl ether acetate were uniformly stirred and mixed. Then, using 0.5 mm diameter zirconia beads, the mixture was dispersed for 3 hours in an Eiger mill (Eiger Japan "Mini Model M-250 MKII"), and filtered through a 5 μm filter to obtain a blue colored composition. The following raw materials were mixed and stirred, and filtered through a 1.0 μm pore size filter to obtain a blue colored curable composition. Blue coloring composition 36.0 parts Alkali-soluble resin solution (1) 8.0 parts Polymerizable compound (M-402) 3.8 parts Photopolymerization initiator (compound represented by formula (301)) 0.8 parts Leveling agent (BYK-330 solution) 1.8 parts PGMAc 49.6 parts

[0272] <Fabrication and evaluation of color filters> A color-curable color filter composition (R-1) was applied to a glass substrate with a black matrix using a slit die coater, and then pre-baked on a 90°C hot plate for 2 minutes to form a coating. Next, after the substrate with the coating was cooled to room temperature, the coating was exposed to radiation containing wavelengths of 365 nm, 405 nm, and 436 nm at an exposure dose of 1,000 J / m2 using a high-pressure mercury lamp through a striped photomask. After alkaline development, the substrate was washed with ultrapure water, and then post-baked at 230°C for 20 minutes to form red striped pixels on the substrate. Next, using a similar method, green striped pixels were formed next to the red striped pixels using a green colored curable composition. Furthermore, blue striped pixels adjacent to the red and green pixels were similarly formed using a blue colored curable composition. Next, a protective film was formed on the pixels, which consisted of three colors: red, green, and blue, using a photocurable resin composition. In this way, an RGB three-color filter with good quality, including contrast ratio, was created. This color filter is suitable for use in solid-state image sensors, image display devices, and the like.

Claims

1. A coloring composition for color filters comprising a pigment (A), a dye derivative (B), a resin-type dispersant (C), and an organic solvent (D), wherein the dye derivative (B) comprises a compound having a heterocycle represented by the following general formula (1) (B1), a compound having a heterocycle represented by the following general formula (2) (B2), and a compound having a heterocycle represented by the following general formula (3) (B3), and the mass ratio of compounds (B1) to (B3) satisfies the range of the following formulas [1] to [3]. [1] (B1) / ((B1)+(B2)+(B3))=80.0-99.0% [2] (B2) / ((B1)+(B2)+(B3))=0.5-10.0% [3] (B3) / ((B1)+(B2)+(B3))=0.5-10.0% General formula (1) 【Chemistry 1】 [In general formula (1), R １ ~R ９ Each of these independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxy group. １ - NHSO ２ - or -NHCO- represents X ２ X represents an optionally substituted alkylene group, an optionally substituted arylene group, or an optionally substituted heterocyclic residue. ３ This represents -NH- or -O-. A and B are each independently —O—(CH ２ )n—R １１ , —OR １２ , —NR １３ R １４ , —Cl, —F, —Y １ —Y ２ —NR １５ R １６ and represent a group selected from these. R １１ R represents a heterocyclic residue which may have substituents. １２ ~ １４ Each of these independently represents a hydrogen atom, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxy group. １ represents -NH- or -O-, Y ２ R represents an optionally substituted alkylene group or an optionally substituted arylene group. １５ and R １６ Each of these independently represents an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxy group. １５ and R １６ These may combine to form a heterocyclic structure that may contain and be substituted with further nitrogen, oxygen, or sulfur atoms. Either A or B is -O-(CH ２ ) ｎ -R １１ , -OR １２ , -NR １３ R １４ , or -Y １ -Y ２ -NR １５ R １６ That is the case. General formula (2) 【Chemistry 2】 [In general formula (2), R ２１ ~R ２５ Each of these independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxy group. ２６ X represents a methyl group. ４ - NHSO ２ - or -NHCO- represents X ５ X represents an optionally substituted alkylene group, an optionally substituted arylene group, or an optionally substituted heterocyclic residue. ６ This represents -NH- or -O-. A and B represent those defined by general formula (1), and either A or B is -O-(CH ２ ) ｎ -R １１ , -OR １２ , -NR １３ R １４ , or -Y １ -Y ２ -NR １５ R １６ That is the case. General formula (3) 【Transformation 3】 [In general formula (3), R ４１ ~ ４４ , R ４６ ~ ５０ Each of these independently represents a hydrogen atom, a halogen atom, a hydroxyl group, an optionally substituted alkyl group, an optionally substituted aryl group, or an optionally substituted alkoxy group. ４５ X represents a carboxyl group. ７ - NHSO ２ - or -NHCO- represents X ８ X represents an optionally substituted alkylene group, an optionally substituted arylene group, or an optionally substituted heterocyclic residue. ９ This represents -NH- or -O-. A and B represent those defined by general formula (1), and either A or B is -O-(CH ２ ) ｎ -R １１ , -OR １２ , -NR １３ R １４ , or -Y １ -Y ２ -NR １５ R １６ That is the case.

2. The coloring composition for color filters according to claim 1, characterized in that the resin-type dispersant (C) contains an acidic resin-type dispersant having an aromatic carboxyl group.

3. A colored curable composition for color filters, characterized by comprising the colored composition for color filters described in claim 1, a photopolymerization initiator (E), and a photopolymerizable compound (F).

4. A color filter comprising a filter segment formed from the colored composition for color filters described in claim 1, or the colored curable composition for color filters described in claim 3.

5. A solid-state image sensor characterized by comprising the color filter described in claim 4.

6. An image display device characterized by comprising the color filter described in claim 4.

Images