Coloring composition for color filter, color filter, liquid crystal display device, and solid-state imaging element

Abstract

To provide a coloring composition for a color filter which has low viscosity and high storage stability even under temperature fluctuation, has good filtration property and light resistance, suppresses crystalline foreign matters, and is excellent in water stain and a pattern shape, a color filter, and a liquid crystal display device and a solid-state imaging element which have the same.SOLUTION: A coloring composition for a color filter contains a red pigment (A), a dye derivative (B), a binder resin (C), and an organic solvent (D), wherein the dye derivative (B) contains any one of a quinophthalone-based dye derivative represented by general formula (1), a quinoline-based dye derivative (B2) represented by general formula (2), and a quinoline-based dye derivative (B3) represented by general formula (3), and the organic solvent (D) contains an organic solvent (D1) having a hydroxyl group having a boiling point of 100°C to 200°C.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a colored composition for a color filter, a color filter, a liquid crystal display device, and a solid-state imaging device.

Background Art

[0002] A color liquid crystal display device is a display device that performs display by controlling the degree of polarization of light passing through a first polarizing plate by a liquid crystal layer sandwiched between two polarizing plates and controlling the amount of light passing through the second polarizing plate. A color filter is provided between the two polarizing plates of the liquid crystal display device, enabling color display. Therefore, liquid crystal display devices have been developed for use in televisions and personal computer monitors.

[0003] Quality items required for a colored composition for a color filter include contrast ratio and luminance. In recent years, quality items such as filterability and crystalline foreign matter have also become more important. In the production of a colored composition for a color filter, there is a filtration step in the final process. If coarse particles remain, the filtration filter must be frequently replaced, and the filtration processing speed will be significantly reduced. In addition, in the post-baking step in the color filter manufacturing process, especially red pigments have the problem of generating crystalline foreign matter.

[0004] Generally, in a pigment dispersion method using a pigment excellent in heat resistance and weather resistance as a colorant, it is difficult to disperse fine pigment particles in a colorant carrier such as a varnish to obtain a stable colored composition. The pigment particles therein often aggregate over time, or a phenomenon called over-dispersion may occur, in which primary particles are crushed and the particle diameter becomes finer than the primary particle diameter, exposing the active surface. A colored composition in which pigment particles have aggregated significantly reduces the filterability, and an over-dispersed colored composition generates crystalline foreign matter. As a result, productivity and quality are significantly reduced. Therefore, high filterability and suppression of crystalline foreign matter are very important.

[0005] In recent years, the pixel size of liquid crystal display devices has been reduced. For finer foreign matter removal, the pore size of the filter has become smaller, and extremely high-level filtration performance is required. In addition, they are now used in various environments, and high light resistance is also demanded. Furthermore, customers who want to reduce the risk of failure in production lines and refrigerators require storage stability under temperature fluctuations. Patent Document 1 discloses quinophthalone-based pigment derivatives excellent in dispersibility, contrast, heat resistance, and lightness, but there is no description regarding filtration performance, light resistance, or storage stability under temperature changes.

Prior Art Documents

Patent Documents

[0006]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0007] The problem to be solved by the present invention is to provide a coloring composition for a color filter, a color filter, a liquid crystal display device including the same, and a solid-state imaging device, which have low viscosity, high storage stability even under temperature fluctuations, good filtration performance and light resistance, suppress crystalline foreign matter, and are excellent in water bleeding and pattern shape.

Means for Solving the Problems

[0008] As a result of intensive research, the present inventors have found that a coloring composition for a color filter having storage stability and filtration performance even under temperature changes can be obtained by using a red pigment, a specific pigment derivative, and a specific organic solvent, and thus have arrived at the present invention.

[0009] That is, the present invention is a coloring composition for a color filter containing a red pigment (A), a pigment derivative (B), a binder resin (C), and an organic solvent (D), The pigment derivative (B) contains either a quinophthalone-based pigment derivative (B1) represented by the following general formula (1) and a quinoline-based pigment derivative (B2) represented by the following general formula (2) or a quinoline-based pigment derivative (B3) represented by the following general formula (3). The present invention relates to a colored composition for a color filter, characterized in that the organic solvent (D) contains an organic solvent (D1) having a hydroxyl group and a boiling point of 100°C to 200°C.

[0010] General formula (1) [Chemical formula] [In general formula (1), R1 to R 13 each independently represents 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, an alkoxyl group which may have a substituent, -SO3H, -COOH, a metal salt of -SO3H or -COOH, or an alkylammonium salt of -SO3H or -COOH. However, at least one of R1 to R 13 is -SO3H, -COOH, a metal salt of -SO3H or -COOH, or an alkylammonium salt of -SO3H or -COOH.]

[0011] General formula (2) [Chemical formula] [In general formula (2), R 21 to R 33 each independently represents 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, an alkoxyl group which may have a substituent, -SO3H, -COOH, a metal salt of -SO3H or -COOH, or an alkylammonium salt of -SO3H or -COOH. However, at least one of R 21 to R 33 is -SO3H, -COOH, a metal salt of -SO3H or -COOH, or an alkylammonium salt of -SO3H or -COOH.]

[0012] General formula (3) [Chemical formula] [In general formula (3), R 41 ~R 53 each independently represents 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, an alkoxyl group which may have a substituent, -SO3H, -COOH, a metal salt of -SO3H or -COOH, or an alkylammonium salt of -SO3H or -COOH. However, at least one of R 41 ~R 53 is -SO3H, -COOH, a metal salt of -SO3H or -COOH, or an alkylammonium salt of -SO3H or -COOH.]

[0013] Furthermore, the present invention relates to the coloring composition for a color filter, characterized in that the quinophthalone-based dye derivative (B1), the quinoline-based dye derivative (B2), and the quinoline-based dye derivative (B3) satisfy the mass ratio of the following formula [1]. [1] 10% ≤ mass of (B1) / (mass of (B1) + mass of (B2) + mass of (B3)) ≤ 90%

[0014] Furthermore, the present invention relates to the coloring composition for a color filter, characterized in that the content of the organic solvent (D1) is 1 to 30% by mass in the organic solvent (D).

[0015] Furthermore, the present invention relates to the coloring composition for a color filter, characterized by further containing a resin-type dispersant (E) having a basic group.

[0016] Furthermore, the present invention relates to the coloring composition for a color filter, characterized in that the resin-type dispersant (E) having a basic group contains at least one selected from the group consisting of structural units represented by the following general formula (4), general formula (5), and general formula (6) and is an acrylic block copolymer.

[0017] General formula (4)

Chem.

[0018] General formula (5)

Chem.

[0019] General formula (6)

Chem.

[0020] The present invention also relates to the color filter coloring composition, characterized in that the binder resin (C) contains a binder resin (C1) containing an alicyclic hydrocarbon-containing monomer unit (c1) and a polymerizable unsaturated group-containing monomer unit (c2).

[0021] The present invention also relates to the color filter coloring composition, characterized in that the red pigment (A) is any one or more selected from the group consisting of diketopyrrolopyrrole-based pigments, azo-based pigments, and anthraquinone-based pigments.

[0022] The present invention also relates to the color filter coloring composition, further characterized by containing a photopolymerizable monomer and / or a photoinitiator.

[0023] The present invention also relates to a color filter comprising a filter segment formed from the color filter coloring composition.

[0024] The present invention also relates to a liquid crystal display device, characterized by comprising the color filter.

[0025] The present invention also relates to a solid-state imaging device, characterized by comprising the color filter.

Advantages of the Invention

[0026] According to the present invention, it is possible to provide a color filter coloring composition, a color filter, a liquid crystal display device, and a solid-state imaging device that have low viscosity, high storage stability even under temperature fluctuations, good filterability and light resistance, suppress crystalline foreign matters, and are excellent in water bleeding and pattern shape.

Brief Description of the Drawings

[0027]

Figure 1

Best Mode for Carrying Out the Invention

[0028] The terms used in this specification are defined below. When expressed as “(meth)acryloyl,” “(meth)acrylic,” “(meth)acrylic acid,” “(meth)acrylate,” or “(meth)acrylamide,” unless otherwise specified, they represent “acryloyl and / or methacryloyl,” “acrylic and / or methacrylic,” “acrylic acid and / or methacrylic acid,” “acrylate and / or methacrylate,” or “acrylamide and / or methacrylamide,” respectively. “C.I.” mentioned in this specification means Color Index (C.I.). The colorant includes pigments and dyes.

[0029] <Red Pigment (A)> The colorant composition for a color filter of the present invention contains a red pigment (A).

[0030] Examples of the red pigment (A) include C.I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 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, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, the pigments described in JP-A No. 2014-134712, the pigments described in Patent No. 6368844, and the like.

[0031] Among the red pigments, in view of the relationship with the color characteristics of the quinophthalone-based dye derivative (B1), quinoline-based dye derivative (B2), and quinoline-based dye derivative (B3) described later, it is preferable to use any one pigment selected from the group consisting of diketopyrrolopyrrole-based pigments, azo-based pigments, and anthraquinone-based pigments alone or in combination of two or more. Further, among these, anthraquinone-based pigments are particularly preferable.

[0032] <Other colorants> The colorant composition for a color filter of the present invention may be used in combination with a colorant other than the above red pigment (A) within a range that does not impair the effects of the present invention, for example, for adjusting chromaticity.

[0033] (Pigment) Examples of the pigment include the following. Orange pigments such as C.I. Pigment Orange 43, 71, or 73 and / or yellow pigments such as C.I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 193, 194, 198, 199, 213, 214, 218, 219, 220, 221, 231, 233 or 234; blue pigments such as C.I. Pigment 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, 79; purple pigments such as C.I. 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, 50; and green pigments such as C.I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, and the pigment described in JP-A-2017-111398 can be used in combination.

[0034] Other preferred colorants include C.I. Pigment Yellow 138, 139, 150, 185, and 231.

[0035] (Dye) Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, building dyes, sulfur dyes, etc. Also included are derivatives of dyes and lake pigments obtained by lake-forming dyes.

[0036] Furthermore, dyes include acid dyes having acidic groups such as sulfonic acid and carboxylic acid; in the case of direct dyes, inorganic salts of acid dyes; salt-forming compounds of acid dyes with quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, or primary amine compounds; salt-forming compounds of these resin components having amino groups with acid dyes, etc. Salt-forming compounds of acid dyes with compounds having an onium base are also preferred because of their excellent fastness. Note that as the compound having an onium base, a resin having a cationic group in the side chain is preferred.

[0037] Basic dyes include salt-forming compounds with organic acids, perchloric acid, or metal salts thereof. Among the salt-forming compounds, the salt-forming compounds of basic dyes are preferred because of their excellent various resistances and compatibility with pigments.

[0038] The chemical structures of the dyes include, for example, azo dyes, disazo dyes, azomethine dyes (such as indoaniline dyes and indophenol dyes), dipyrromethene dyes, quinone dyes (such as benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, and anthrapyridone dyes), carbonium dyes (such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, and acridine dyes), quinoneimine dyes (such as oxazine dyes and thiazine dyes), azine dyes, polymethine dyes (such as oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, and croconium dyes), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and the like. Among these, from the viewpoint of color characteristics such as hue, color separation property, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred. The specific structures of the dyes are described in "New Edition Dye Handbook" (edited by the Organic Synthetic Chemistry Association; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), "Pigment Handbook" (edited by Ohkawara et al.; Kodansha, 1986), and the like.

[0039] In the present invention, when other colorants other than the red pigment (A) are used in combination, the red pigment (A) is preferably in the range of 40% by mass to 100% by mass based on the total amount of the colorants (100% by mass). More preferably, it is in the range of 50% by mass to 100% by mass. When the red pigment (A) is 40% by mass or more, the storage stability is excellent.

[0040] (Micronization of the pigment) When using a pigment as a colorant, it is preferable to perform a micronization treatment and then mix it with other raw materials. Examples of the micronization treatment method include wet grinding, dry grinding, solution precipitation method, etc. Among these, salt milling treatment by a kneader method, which is a type of wet grinding, is preferable. The average primary particle size of the pigment after the micronization treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. With an appropriate particle size, the dispersibility is further improved, and the contrast ratio of the coating film is further improved. The average primary particle size is the average value of about 20 particles arbitrarily selected from the enlarged image of a TEM (transmission electron microscope). When there are a longitudinal axis length and a transverse axis length of the particle, the longitudinal axis length is used.

[0041] Salt milling treatment is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while heating using a batch-type or continuous kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, a planetary mixer, etc., and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, a pigment with a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution can be obtained.

[0042] Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate, etc. Among these, sodium chloride (table salt) is preferable from the viewpoint of price. The amount of the water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, more preferably 300 to 1000 parts by mass, based on 100 parts by mass of the pigment, from both the treatment efficiency and the production efficiency aspects.

[0043] The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound that dissolves (mixes) in water and does not substantially dissolve the water-soluble inorganic salt. As for the water-soluble organic solvent, a high-boiling solvent with a boiling point of 120 °C or higher is preferable in that it is difficult to volatilize due to the temperature rise during salt milling. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, and the like. The usage amount of the water-soluble organic solvent is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the pigment.

[0044] During the salt milling treatment, a resin can be added as needed. Examples of the resin include natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like. The resin is preferably solid at room temperature and water-insoluble, and more preferably partially soluble in the water-soluble organic solvent. The usage amount of the resin is preferably 5 to 200 parts by mass, based on 100 parts by mass of the pigment.

[0045] <Dye Derivative (B)>

[0046] The coloring composition for a color filter of the present invention contains, as the dye derivative (B), either a quinophthalone-based dye derivative (B1) represented by the following general formula (1), a quinoline-based dye derivative (B2) represented by the following general formula (2), or a quinoline-based dye derivative (B3) represented by the following general formula (3).

[0047] General formula (1) [Chemical formula] [In general formula (1), R1 to R 13 each independently represents 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, an alkoxyl group which may have a substituent, -SO3H, -COOH, a metal salt of -SO3H or -COOH, or an alkylammonium salt of -SO3H or -COOH. However, at least one of R1 to R 13 is -SO3H, -COOH, a metal salt of -SO3H or -COOH, or an alkylammonium salt of -SO3H or -COOH.]

[0048] General formula (2) [Chemical formula] [In general formula (2), R 21 to R 33 each independently represents 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, an alkoxyl group which may have a substituent, -SO3H, -COOH, a metal salt of -SO3H or -COOH, or an alkylammonium salt of -SO3H or -COOH. However, at least one of R 21 to R 33 is -SO3H, -COOH, a metal salt of -SO3H or -COOH, or an alkylammonium salt of -SO3H or -COOH.]

[0049] General formula (3) [Chemical formula] [In general formula (3), R 41 to R 53 each independently represents 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, an alkoxyl group which may have a substituent, -SO3H, -COOH, a metal salt of -SO3H or -COOH, or an alkylammonium salt of -SO3H or -COOH. However, at least one of R 41 to R 53At least one of them is -SO3H, -COOH, a metal salt of -SO3H or -COOH, or an alkylammonium salt of -SO3H or -COOH.

[0050] In the present invention, by using a quinophthalone-based dye derivative (B1) and a quinoline-based dye derivative (B2) or (B3) in combination as the dye derivative (B), compared with the case of using a conventionally known derivative, a coloring composition for a color filter having high storage stability and good compatibility even under temperature fluctuations can be provided. Although the reason for this is not clear, the present inventor considers as follows.

[0051] The coloring composition for a color filter of the present invention contains a dispersion medium such as a binder resin and an organic solvent described later, and various additives. Compounds having various polarities and physical properties are selected as the binder resin and additives used at this time according to the required functions. Dye derivatives having many aromatic groups and cyclic structures, such as quinophthalone-based dye derivatives (B1), have high hydrophobicity and high affinity with red pigments (A) and highly hydrophobic dispersion media and additives, while having low affinity with highly hydrophilic dispersion media and additives. Therefore, in applications that require highly hydrophilic dispersion media and additives, the storage stability deteriorates in a harsh environment where the temperature fluctuates. Also, dye derivatives having many carboxy groups, amide groups, and carbonyl groups, such as quinoline-based dye derivatives (B2) and (B3), have high affinity with highly hydrophilic dispersion media and additives, while having low affinity with red pigments (A) and highly hydrophobic dispersion media and additives. Therefore, in applications that require highly hydrophobic dispersion media and additives, the storage stability deteriorates in a harsh environment where the temperature fluctuates. Thus, by using at least two of a quinophthalone-based dye derivative (B1) and a quinoline-based dye derivative (B2) or (B3) having different affinities for various dispersion media and additives in combination, the compatibility with various compounds contained as a coloring composition for a color filter becomes good, and it is considered that the storage stability is good even in a harsh environment where the temperature fluctuates.

[0052] In addition, for the dye derivative (B) used in the coloring composition for a color filter of the present invention, it is preferable that the mass ratio of the quinophthalone-based dye derivative (B1) to the quinoline-based dye derivatives (B2) and (B3) satisfies the following formula [1]. [1] 10% ≦ mass of (B1) / (mass of (B1) + mass of (B2) + mass of (B3)) ≦ 90%

[0053] As the range of formula [1], more preferably, [1] 25% ≦ mass of (B1) / (mass of (B1) + mass of (B2) + mass of (B3)) ≦ 75% That is. By setting the mass ratio of the quinophthalone-based dye derivative (B1), the quinoline-based dye derivatives (B2) and (B3) within the above range, a coloring composition for a color filter with high storage stability can be obtained even under temperature fluctuations.

[0054] The method for synthesizing the quinophthalone-based dye derivative (B1) is not particularly limited, and examples include a method of reacting sulfuric acid with C.I. Pigment Yellow 138 as disclosed in Example 1 of Patent 4585781. Also, the method for synthesizing the quinoline-based dye derivatives (B2) and (B3) is not particularly limited, and examples include a method of reacting sulfuric acid with C.I. Pigment Yellow 138 and then heating and stirring under alkaline conditions as disclosed in Patent 4396210. When the synthesized compound contains impurities, the impurities may be removed by recrystallization, reprecipitation, filtration, washing, preparative liquid chromatography, or the like.

[0055] The mass ratio of the red pigment (A) to the dye derivative (B) is preferably in the range of (A):(B) = 70:30 to 98:2, and more preferably in the range of (A):(B) = 80:20 to 95:5. When the ratio of the dye derivative (B) is within this range, it is excellent in storage stability, filterability, and light resistance.

[0056] Examples of the quinophthalone-based pigment derivative (B1) include the following structures.

[0057]

Chem.

[0058]

Chem.

[0059]

Chem.

[0060]

Chem.

[0061] Examples of the quinoline-based pigment derivative (B2) include the following structures.

[0062]

Chem.

[0063]

Chem.

[0064]

Chem.

[0065]

Chem.

[0066] Examples of the quinoline-based pigment derivative (B3) include the following structures.

[0067]

Chem.

[0068]

Chem.

[0069]

Chem.

[0070]

Chem.

[0071] (Other dye derivatives) Examples of dye derivatives other than quinophthalone-based dye derivatives (B1), quinoline-based dye derivatives (B2), and quinoline-based dye derivatives (B3) include compounds in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent is introduced into a pigment, anthraquinone, acridone, or triazine. For example, those described in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, JP-A-2001-335717, JP-A-2003-128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094873, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916, Japanese Patent No. 4585781, etc. can be used, and one or more of these may be used in combination with quinophthalone-based dye derivatives (B1), quinoline-based dye derivatives (B2), and quinoline-based dye derivatives (B3).

[0072] <Binder resin (C)> The colorant composition for a color filter of the present invention contains a binder resin (C).

[0073] The binder resin (C) is a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm. The transmittance is preferably 95% or more. In terms of curability, the binder resin (C) includes, for example, thermoplastic resins, thermosetting resins, active energy ray curable resins, and the like. The active energy ray curable resin may have an active energy ray reactive functional group in the thermoplastic resin or the thermosetting resin. In terms of physical properties, the binder resin (C) is preferably an alkali-soluble resin from the viewpoint of developability. Alkali solubility is for imparting developability in the alkali development step during the production of the color filter, and an acidic group is required.

[0074] The binder resin (C) can be used alone or in combination of two or more.

[0075] The content of the binder resin (C) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on 100 parts by mass of the colorant. When contained in an appropriate amount, a film can be easily formed and good color characteristics are easily obtained.

[0076] (Thermoplastic resin) Examples of the thermoplastic resin include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Examples of the alkali-soluble thermoplastic resin include resins having an acidic group such as a carboxyl group or a sulfonic group. Examples of the alkali-soluble thermoplastic resin include acrylic resins having an acidic group, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers. Among these, acrylic resins having an acidic group and styrene / styrene sulfonic acid copolymers are preferred in terms of improving developability, heat resistance, and transparency.

[0077] (Active energy ray curable alkali-soluble resin) The active energy ray-curable alkali-soluble resin preferably has an ethylenically unsaturated double bond. The ethylenically unsaturated double bond can be introduced, for example, by the methods (i) to (iii) described in the section on binder resin (C1) described later. The resin is three-dimensionally crosslinked by the effect of active energy rays, increasing the crosslink density and improving chemical resistance.

[0078] (Binder resin (C1)) From the viewpoint of suppressing water stains and heat resistance, the binder resin (C) preferably contains a binder resin (C1) containing an alicyclic hydrocarbon-containing monomer unit (c1) and a polymerizable unsaturated group-containing monomer unit (c2). It is presumed that the alicyclic hydrocarbon structure, which is highly hydrophobic and has both flexibility and rigidity, has low affinity with the developer and can form a tough film. It is presumed that the presence of a polymerizable unsaturated group allows the resins to crosslink with each other upon exposure to form a tougher cured film, suppressing water stains and obtaining a pattern with good heat resistance.

[0079] The binder resin (C1) is not particularly limited as long as it is a resin containing an alicyclic hydrocarbon-containing monomer unit (c1) and a polymerizable unsaturated group-containing monomer unit (c2), and known resins can be used. For example, a copolymer of a monomer forming an alicyclic hydrocarbon-containing monomer unit (c1) and a monomer forming a polymerizable unsaturated group-containing monomer unit (c2), or a copolymer of a monomer forming an alicyclic hydrocarbon-containing monomer unit (c1) and another monomer copolymerizable therewith, to which a compound having a polymerizable unsaturated group is reacted to introduce a polymerizable unsaturated group-containing monomer unit (c2), and a copolymer obtained by the method described in JP-A-2008-165059, etc. can be mentioned.

[0080] 〔Alicyclic hydrocarbon-containing monomer unit (c1)〕 Examples of the monomer forming the alicyclic hydrocarbon-containing monomer unit (c1) include isobornyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyl oxyethyl (meth)acrylate, adamantyl (meth)acrylate, etc. Among these, from the viewpoints of suppressing water bleeding and pattern shape, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[0081] From the viewpoints of suppressing water bleeding and pattern shape, the content of the alicyclic hydrocarbon-containing monomer unit (c1) is preferably 1 to 60 mol%, more preferably 1 to 40 mol% in all the constituent units of the binder resin (C1).

[0082] 〔Polymerizable unsaturated group-containing monomer unit (c2)〕 Examples of the method of incorporating the polymerizable unsaturated group-containing monomer unit (c2) into the binder resin (C1) include the following methods (i) to (iii).

[0083] <Method (i)> Method (i) is, for example, first, to synthesize a polymer (precursor) of an epoxy group-containing monomer and other monomers. Next, a carboxyl group-containing monomer (modifying compound) is added to the epoxy group of the precursor.

[0084] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferable from the viewpoint of reactivity.

[0085] Examples of the carboxyl group-containing monomer include acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, fumaric acid, etc. Among these, acrylic acid and methacrylic acid are preferable.

[0086] From the viewpoint of developability, a reaction product of an acid anhydride with a product obtained by adding a carboxyl group of a carboxyl group-containing monomer to an epoxy group of an epoxy group-containing monomer unit is also useful as a polymerizable unsaturated group-containing monomer unit (c2).

[0087] Examples of the acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc.

[0088] <Method (ii)> Method (ii) is, for example, first, to synthesize a polymer (precursor) of a carboxyl group-containing monomer and other monomers. Next, an epoxy group-containing monomer (modifying compound) is added to the carboxyl group of the precursor.

[0089] <Method (iii)> Method (iii) is, for example, first, to synthesize a polymer (precursor) of a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers. Next, the isocyanate group of an isocyanate group-containing monomer (modifying compound) is reacted with the hydroxyl group of the precursor.

[0090] Examples of the hydroxyl group-containing monomer include hydroxyalkyl (meth) acrylates 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.

[0091] Examples of the isocyanate group-containing monomer include 2-(meth) acryloylethyl isocyanate, 2-(meth) acryloyloxyethyl isocyanate, or 1,1-bis [methacryloyloxy] ethyl isocyanate.

[0092] From the viewpoint of the pattern shape, the content of the polymerizable unsaturated group-containing monomer unit (c2) is preferably 5 to 80 mol%, more preferably 10 to 80 mol% in all the constituent units of the binder resin (C1).

[0093] 〔Other monomer unit (c3)〕 The binder resin (C1) can contain monomer units other than (c1) and (c2) (hereinafter also referred to as other monomer units (c3)).

[0094] Examples of the monomer forming the other monomer unit (c3) include (meth) acrylates such as methyl (meth) acrylate, ethyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, t-butyl (meth) acrylate, stearyl (meth) acrylate, phenyl (meth) acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, lauryl (meth) acrylate, 2-ethylhexyl (meth) acrylate, n-hexyl (meth) acrylate, isobutyl (meth) acrylate, 2-methoxyethyl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate; Hydroxyl group-containing (meth)acrylates such as 2-hydroxyethyl methacrylate, 2- or 3-hydroxypropyl methacrylate, and glycerin monomethacrylate; Epoxy group-containing (meth)acrylates such as glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate; Unsaturated carboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, itaconic acid, maleic acid, and fumaric acid; (Meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; Vinyl fatty acids such as vinyl acetate or vinyl propionate; N-substituted maleimides such as phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)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-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine; Phosphoric acid ester group-containing (meth)acrylates such as 2-(meth)acryloyloxyethyl acid phosphate and compounds obtained by reacting a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid with the hydroxyl groups of the above-mentioned hydroxyl group-containing (meth)acrylates; Examples include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate. These monomers can be used alone or in combination of two or more.

[0095] From the viewpoints of suppressing water bleeding and pattern shape, as the other monomer unit (c3), it is preferable that 2-ethylhexyl (meth)acrylate and 2-methoxyethyl (meth)acrylate, which have a low Tg, are contained in an amount of 20 mol% or more in all the constituent units of the binder resin (C1).

[0096] The binder resin (C1) can be used alone or in combination of two or more.

[0097] From the viewpoint of suppressing water bleeding and pattern shape, the content of the binder resin (C1) is preferably 30 to 100% by mass, more preferably 50 to 100% by mass, based on 100% by mass of the binder resin (C).

[0098] (Binder resin (C2)) The colored composition for a color filter of the present invention may contain, as the binder resin (C), a binder resin other than the binder resin (C1) (hereinafter also referred to as the binder resin (C2)).

[0099] <Thermosetting compound> In the present invention, it can further contain a thermosetting compound. When producing a color filter using the colored composition for a color filter of the present invention, by containing a thermosetting compound, it reacts during the firing of the filter segment to increase the crosslink density of the coating film. Therefore, the heat resistance of the filter segment is improved, pigment aggregation during the firing of the filter segment is suppressed, and the effect of improving the contrast ratio can be obtained.

[0100] The thermosetting compound may be a low-molecular compound or a high-molecular compound such as a resin. Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds, but the present invention is not limited thereto. In the colored composition for a color filter of the present invention, epoxy compounds and oxetane compounds are preferably used.

[0101] <Resin-type dispersant> The colorant composition for a color filter of the present invention can contain a resin-type dispersant. As the resin-type dispersant, it has a colorant affinity site having a property of adsorbing to an added colorant and a site compatible with a colorant carrier, and adsorbs to the added colorant to function to stabilize the dispersion in the colorant carrier. Specifically, as the resin-type dispersant, polycarboxylic acid esters such as polyurethane and polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamidophosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, amides formed by the reaction of poly(lower alkyleneimine) and a polyester having a free carboxy group and salts thereof, etc., oil-based dispersants, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc., water-soluble resins and water-soluble polymer compounds, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide adduct compounds, phosphate ester-based, etc. are used, and these can be used alone or in admixture of two or more, but are not necessarily limited thereto.

[0102] Among the above resin-type dispersants, nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, etc. in the side chain, and urethane-based polymer dispersants are well known because the viscosity of the dispersion becomes low and a high contrast ratio is exhibited with a small addition amount.

[0103] The resin-type dispersant is preferably used in an amount of about 5 to 200 parts by mass based on the total amount of the colorant, and more preferably in an amount of about 5 to 100 parts by mass from the viewpoint of film-forming properties.

[0104] (Resin-type dispersant (E) having a basic group) In the present invention, from the viewpoint of affinity with the quinophthalone-based dye derivative (B), it is preferable that the resin-type dispersant contains a resin-type dispersant (E) having a basic group.

[0105] As the resin-type dispersant (E) having a basic group, it is preferable to contain an acrylic block copolymer containing at least one selected from the group consisting of structural units represented by the following general formula (2), general formula (3), and general formula (4).

[0106] The acrylic block copolymer comprises an A block having a structural unit of a quaternary ammonium base represented by the general formula (2) or a primary, secondary or tertiary amino group represented by the general formulas (3) and (4), and a B block not having the structural units represented by the general formulas (2) to (4). The structures of the A block and the B block are not particularly limited, but an A-B block, a B-A-B block, or an A-B-A is preferable, and an A-B block and a B-A-B block can be more preferably used.

[0107] General formula (2)

Chemical formula

[0108] General formula (3)

Chemical formula

[0109] General formula (4) [Chemical formula] (In general formula (4), R7 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxyradical group, or OR 12 represents, and R 12 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group. R8, R9, R 10 , R 11 each independently represent a methyl group, an ethyl group, or a phenyl group. R4 represents a hydrogen atom or a methyl group, and X represents a divalent linking group.)

[0110] As R1 to R3 in general formula (2), an alkyl group having 1 to 4 carbon atoms which may have a substituent and an aralkyl group having 7 to 16 carbon atoms which may have a substituent are more preferable, and a methyl group, an ethyl group, a propyl group, a butyl group, and a benzyl group are particularly preferable. Further, as R5 and R6 in general formula (3), an alkyl group having 1 to 4 carbon atoms which may have a substituent is more preferable, and a methyl group, an ethyl group, a propyl group, and a butyl group are particularly preferable.

[0111] In R7 of general formula (4), examples of the alkyl group having 1 to 18 carbon atoms include linear, branched, and cyclic alkyl groups. Specifically, a methyl group, an ethyl group, a normal propyl group, an isopropyl group, an n-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, an n-octyl group, a hexadecyl group, etc. can be mentioned. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 1-naphthyl group, a 2-naphthyl group, etc. Examples of the aralkyl group having 7 to 12 carbon atoms include a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms. Specifically, a benzyl group, a phenethyl group, an α-methylbenzyl group, a 2-phenylpropan-2-yl group, etc. can be mentioned. Examples of the acyl group include alkanoyl groups having 2 to 8 carbon atoms and aroyl groups, and specific examples include an acetyl group and a benzoyl group. Among these, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an oxy radical group are particularly preferable, a hydrogen atom and a methyl group are more preferable, and a methyl group is most preferable.

[0112] In the general formulas (2), (3) and (4), examples of the divalent linking group X include a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, -CONH-R 13 -, -COO-R 14 -(wherein R 13 and R 14 are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group having 2 to 10 carbon atoms (alkyloxyalkyl group)), and the like, and -COO-R 1 4 - is preferable. Further, in the above formula (2), as the counter anion Y - , Cl - , Br - , I - , ClO4 - , BF4 - , CH3COO - , PF6 - and the like can be mentioned.

[0113] The A block is not particularly limited as long as it has any of the structural units represented by the general formulas (2) to (4), but it is preferably a partial structure derived from an ethylenically unsaturated monomer.

[0114] Specific examples of the ethylenically unsaturated monomer having a quaternary ammonium base, which is a precursor and partial structure of the structural unit represented by the general formula (2), include, for example, alkyl (meth)acrylate quaternary ammonium salts such as (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, (meth)acryloyloxyethyldimethylbenzylammonium chloride, (meth)acryloyloxymethylmorpholinoammonium chloride, etc.; alkyl (meth)acryloylamide quaternary ammonium salts such as (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloylaminoethyltriethylammonium chloride, (meth)acryloylaminoethyldimethylbenzylammonium chloride, etc.; dimethyldiallylammonium methyl sulfate, trimethylvinylphenylammonium chloride, and the like.

[0115] Specific examples of the ethylenically unsaturated monomer having a tertiary amine group, which is a precursor and partial structure of the structural unit represented by the general formula (3), include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N- diethylaminopropyl (meth)acrylate and other (meth)acrylates having a tertiary amino group; N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl (meth)acrylamide and other (meth)acrylamides having a tertiary amino group; and the like. etc. can be mentioned.

[0116] Specific examples of the ethylenically unsaturated monomer that is a precursor and partial structure of the structural unit represented by the general formula (4) include, for example, compounds represented by the following compounds (4-1) to (4-11).

[0117]

Chemical formula

[0118]

Chemical formula

[0119] In compounds (4-1) to (4-11), R4 represents a hydrogen atom or a methyl group.

[0120] Among these, 2,2,6,6-tetramethylpiperidyl methacrylate (the compound in which R4 is a methyl group in the above compound (4-1)), 1,2,2,6,6-pentamethylpiperidyl methacrylate (the compound in which R4 is a methyl group in the above compound (4-2)) are preferred, and particularly 1,2,2,6,6-pentamethylpiperidyl methacrylate is preferred.

[0121] The partial structure containing the structural units represented by the general formulas (2) to (4) may be contained alone or in two or more kinds in one A block. When two or more kinds are contained, they may be contained in any mode of random copolymerization or block copolymerization.

[0122] Also, the content of the structural units represented by the general formulas (2) to (4) in the A block is preferably 50 to 100% by mass, more preferably 80 to 100% by mass, and particularly preferably 95 to 100% by mass.

[0123] On the other hand, the structural unit not containing the structural units represented by the general formulas (2) to (4) in the A block and the B block are not particularly limited as long as they are polymer structures obtained by copolymerizing copolymerizable monomers, and can be appropriately selected according to the use. Copolymerizable monomers are shown below.

[0124] For example, linear or branched alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; Cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate; Heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate and 3-methyl-3-oxetanyl (meth)acrylate; (Meth)acrylates having an aromatic ring such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; (Poly)alkylene glycol monoalkyl ether (meth)acrylates such as 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, tripropylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, polypropylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monolauryl ether (meth)acrylate, polyethylene glycol monostearyl ether (meth)acrylate, and octoxypolyethylene glycol - polypropylene glycol (meth)acrylate; (Poly)alkylene glycol (meth)acrylates having an aromatic ring such as phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, parachlorophenylphenoxyethyl (meth)acrylate, parachlorophenylphenoxyethylene glycol (meth)acrylate, parachlorophenylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, and nonylphenoxypoly(ethylene glycol - propylene glycol)(meth)acrylate; (Meth)acrylates having an alkyloxysilyl group such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate; (Meth)acryloxy-modified polydimethylsiloxanes (silicone macromers); N-substituted (meth)acrylamides such as (meth)acrylamide, dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, and acryloylmorpholine; and nitriles such as (meth)acrylonitrile, etc. Also, styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate, etc.

[0125] Furthermore, a carboxyl group-containing ethylenically unsaturated monomer can also be used in combination. Examples of the carboxyl group-containing ethylenically unsaturated monomer include (meth)acrylic acid, (meth)acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth)acrylate, and ω-carboxypolycaprolactone (meth)acrylate, etc.

[0126] Also, within a range not impairing the effects of the present invention, an ethylenically unsaturated monomer containing an amino group other than the structural units represented by general formulas (2) to (4) may be used in combination.

[0127] The B block is preferably a partial structure derived from an ethylenically unsaturated monomer, and further, an ethylenically unsaturated monomer selected from the group consisting of at least benzyl (meth) acrylate, methyl (meth) acrylate, ethyl (meth) acrylate, and hydroxyethyl (meth) acrylate is preferably used.

[0128] (Production of acrylic block copolymer) The acrylic block copolymer that can be used in the present invention is prepared, for example, by the living polymerization method shown below. Here, living polymerization is a polymerization method in which side reactions occurring in general radical polymerization are suppressed, and further, the growth of polymerization occurs uniformly, so that block polymers and resins with uniform molecular weights can be easily synthesized. Depending on the charging ratio of the polymerization initiator and the vinyl monomer added during polymerization, the molecular weight of the polymer and the ratio of the monomers for block copolymerization can be freely controlled, and it can be used for the production of block polymers, gradient polymers, star polymers, comb-shaped polymers, and further, end-functional polymers.

[0129] The acrylic block copolymer in the present invention can be synthesized by a known radical living polymerization method, and the method described in JP-A-2014-219665 or the like can be used. The atom transfer radical polymerization method (ATRP method) and the nitroxide method (NMP method) are preferable not only from the viewpoint of controlling the molecular weight and molecular weight distribution of the polymer, but also in terms of being applicable to a wide range of monomers and being able to adopt a polymerization temperature adaptable to existing equipment. Further, the nitroxide method (NMP method) is more preferable in that it does not use transition metals or the like that can cause coloring or the like.

[0130] [Atom transfer radical polymerization method (ATRP method)] In the atom transfer radical polymerization method, it is carried out using transition metal complexes such as copper, ruthenium, iron, nickel, etc. as redox polymerization catalysts. Specific examples of the transition metal complexes include low-valent halogenated transition metals such as copper(I) chloride and copper(I) bromide.

[0131] An organic ligand is used for the above transition metal complex. The organic ligand is used to enable solubility in the polymerization solvent and reversible changes of the redox polymerization catalyst. Examples of the coordination atoms of the transition metal include nitrogen atom, oxygen atom, phosphorus atom, sulfur atom, etc.

[0132] As the initiator used in the atom radical polymerization method, known ones can be used, but mainly organic halides having highly reactive carbon-halogen bonds, sulfonyl halide compounds, etc. are used. Specifically exemplified are ethyl bromoisobutyrate, ethyl bromobutyrate, ethyl chloroisobutyrate, ethyl chlorobutyrate, p-toluenesulfonyl chloride, 1-bromoethylbenzene, chloroethylbenzene, etc. These are used alone or in combination.

[0133] [Nitroxide method (NMP method)] The living radical polymerization method via nitroxide is carried out using a stable nitroxyl free radical (=N−O·) as a radical capping agent. The stable nitroxyl free radical is not particularly limited, and examples include 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), 2,2,6,6-tetraethyl-1-piperidinyloxy radical, 2,2,6,6-tetramethyl-4-oxo-1-piperidinyloxy radical, 2,2,5,5-tetramethyl-1-pyrrolidinyloxy radical, 1,1,3,3-tetramethyl-2-isoindolinyl-oxy radical, N,N-di-t-butylamine oxy radical, etc. Instead of the nitroxyl free radical, a stable free radical such as galvinoxyl free radical may be used.

[0134] The above radical capping agent is used in combination with a radical polymerization initiator. The combined ratio of the two is not particularly limited, but 0.1 to 10 moles of the radical initiator is suitable for 1 mole of the radical capping agent.

[0135] The above radical polymerization initiator is appropriately selected according to the weight average molecular weight (Mw) of the resin to be synthesized. However, it is used in a ratio of 0.0001 to 1 mole, preferably 0.001 to 0.1 mole, per 1 mole of the (meth)acryloyl group in the monomer used when synthesizing the acrylic block copolymer.

[0136] As the radical polymerization initiator, known ones can be used, and there is no particular limitation as long as it is a compound capable of generating radicals under the polymerization temperature conditions. For example, dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, t-butyl cumyl peroxide, α,α'-bis(t-butylperoxy-m-isopropyl)benzene, 2,5-di(t-butylperoxy)hexyne-3; Peroxy esters such as t-butyl peroxybenzoate, t-butyl peroxyacetate, 2,5-dimethyl-2,5-di(benzoylperoxy)hexane; Ketone peroxides such as cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide; Peroxyketals such as 2,2-bis(4,4-di-t-butylperoxycyclohexyl)propane, 1,1-bis(t-butylperoxy)3,3,5-trimethylcyclohexane, 1,1-bis(t-butylperoxy)cyclohexane, n-butyl-4,4-bis(t-butylperoxy)valerate; Hydroperoxides such as cumene hydroperoxide, diisopropylbenzene hydroperoxide, 2,5-dimethylcyclohexane-2,5-dihydroperoxide; Diacyl peroxides such as benzoyl peroxide, decanoyl peroxide, lauroyl peroxide, 2,4-dichlorobenzoyl peroxide; Organic peroxides such as peroxydicarbonates such as bis(t-butylcyclohexyl) peroxydicarbonate, or mixtures thereof may be mentioned.

[0137] Also, an azo compound can also be used as a radical polymerization initiator. For example, 2,2'-azobisbutyronitriles such as 2,2'-azobisisobutyronitrile (AIBN), 2,2'-azobis(2-methylbutyronitrile), 2,2'-azobisvaleronitriles such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), 2,2'-azobispropionitriles such as 2,2'-azobis(2-hydroxymethylpropionitrile), 1,1'-azobis-1-alkanenitriles such as 1,1'-azobis(cyclohexane-1-carbonitrile) can be used.

[0138] Furthermore, as reported in Macromolecules 1995, 28, 2993 instead of using a radical capping agent and the above radical polymerization initiator in combination, an alkoxyamine compound represented by the following compounds (N-1 to 4) may be used as an initiator.

[0139] (N-1)

Chemical formula

[0140] (N-2)

Chemical formula

[0141] (N-3)

Chemical formula

[0142] (N - 4) [Chemical formula]

[0143] In the process of producing an acrylic block copolymer, a solventless or solvent can be used depending on the case. Examples of the solvent include ethyl acetate, n-butyl acetate, isobutyl acetate, toluene, xylene, acetone, hexane, methyl ethyl ketone, cyclohexanone, propylene glycol monomethyl ether acetate, dipropylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, ethylene glycol monobutyl ether acetate, diethylene glycol monoethyl ether acetate, or diethylene glycol monobutyl ether acetate, etc., but are not particularly limited thereto. These polymerization solvents may be used as a mixture of two or more kinds.

[0144] The amount of the solvent used is preferably 0 to 300 parts by mass, more preferably 0 to 100 parts by mass, based on 100 parts by mass of the monomers composed of block A and block B. The solvent used can be removed by operations such as distillation after the reaction is completed, or can be used as it is as part of the product of the composition.

[0145] The content of block A in the acrylic block copolymer solid content is preferably 1 to 99% by mass, more preferably 20 to 50% by mass, and particularly preferably 20 to 30% by mass. When block A contains 20 to 30% by mass, the remaining 70 to 80% by mass constitutes block B. Therefore, since block B has an affinity for the solvent which is the dispersion medium, the pigment can be stably present in the dispersion medium.

[0146] In addition, the amount of the structural units represented by general formulas (2) to (4) in 1 g of the acrylic block copolymer that can be used in the present invention is preferably usually 0.1 to 5 mmol, and within this range, lightness and dispersibility can be better balanced.

[0147] Although it depends on the types of the structural units represented by general formulas (2) to (4), the acrylic block copolymer in the present invention more preferably has an amine value of 30 to 350 mgKOH / g. When the amine value is 30 mgKOH / g or more, the viscosity and storage stability of the coloring composition are excellent, and when it is 350 mgKOH / g or less, the lightness is excellent.

[0148] In addition, the molecular weight of the acrylic block copolymer in the present invention is preferably in the range of usually 1,000 or more and 100,000 or less in terms of weight average in terms of polystyrene. When the molecular weight of the acrylic block copolymer is less than 1,000, the dispersion stability decreases, and when it exceeds 100,000, the developability tends to decrease.

[0149] <Organic solvent (D)> (Organic solvent (D1)) The organic solvent (D) used in the present invention is characterized by containing an organic solvent (D1) having a hydroxyl group and a boiling point of 100°C to 200°C at 760 mmHg. By using this specific organic solvent having a boiling point and structure, the affinity of the red pigment (A) and the quinophthalone-based pigment derivative (B1), quinoline-based pigment derivative (B2), and quinoline-based pigment derivative (B3) contained in the coloring composition becomes better, the generation of foreign matters can be suppressed, and high stability and filterability can be exhibited as the coloring composition.

[0150] In addition, when an organic solvent having a boiling point of 100°C or higher is used, appropriate drying properties are obtained, and changes in the solvent composition ratio and non-volatile content are less likely to occur during production, storage, and use, which is preferable. When an organic solvent having a boiling point of 200°C or lower is used, it is easy to dry when forming a thin film of the coloring composition. Therefore, when the coating liquid is applied by the spin coating method, it is difficult to form a liquid bulge at the end of the substrate, and in the drying process from the end of the spin to the drying process, the bulged part of the liquid smoothly progresses from the end of the substrate toward the center, so that a frame-shaped color unevenness (film thickness unevenness) is difficult to form. Further, also in the die coating method, since it is difficult to form a bulged part of the liquid at the coating boundary part, there is an effect that a frame-shaped color unevenness (film thickness unevenness) is difficult to form due to the smooth progress from the boundary part toward the center.

[0151] In the present invention, the content of the organic solvent (D1) is preferably 1 to 30% by weight, more preferably 5 to 20% by weight, based on the total amount of the organic solvent (D) (100% by weight). When the content of the organic solvent (D1) is within this range, the storage stability and filterability are excellent.

[0152] When the organic solvent (D1) is exemplified together with <boiling point (°C)>, ethylene glycol monobutyl ether acetate <188>, ethylene glycol monomethyl ether acetate <145>, cyclohexanol acetate <173>, cyclohexanone <155>, propylene glycol diacetate <190>, propylene glycol monomethyl ether <121>, 3-methoxybutanol <161>, etc. can be mentioned. Particularly preferred solvents include propylene glycol monomethyl ether, 3-methoxybutanol, etc.

[0153] (Other organic solvents) In the present invention, the following organic solvents can be used as the organic solvents other than the organic solvent (D1). For example, propylene glycol monomethyl ether acetate, ethyl lactate, benzyl alcohol, 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol,, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, 3-methyl-1,3-butanediol,, 3-methoxy-3-methylbutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,Organic solvents such as N-dimethylformamide, n-butylbenzene, n-propyl acetate, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoteritary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diisobutyl ketone, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, benzyl alcohol, methyl isobutyl ketone, n-amyl acetate, n-butyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester, etc. can also be used.,

[0154] <Photopolymerizable monomer> The colored composition for a color filter of the present invention can be made into a photosensitive colored composition by containing a photopolymerizable monomer and / or a photopolymerization initiator. The photopolymerizable monomer includes monomers or oligomers that are cured by ultraviolet rays, heat, etc. to form a transparent resin.

[0155] The photopolymerizable monomer includes, 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, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylate of methylolated melamine, epoxy (meth)acrylate, urethane acrylate and other various acrylate esters and methacrylate esters, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile and the like.

[0156] (Photopolymerizable monomer having an acid group) The photopolymerizable monomer can contain a photopolymerizable monomer having an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, a phosphoric acid group and the like.

[0157] The photopolymerizable monomer having an acid group includes, for example, esterified products of polyhydric alcohols and free hydroxyl group-containing poly(meth)acrylates of (meth)acrylic acid and dicarboxylic acids; esterified products of polyvalent carboxylic acids and monohydroxyalkyl (meth)acrylates, etc. Specific examples include free carboxyl group-containing monoesterified products of monohydroxy oligoacrylates or monohydroxy oligo(meth)acrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc., and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid; free carboxyl group-containing oligoesterified products of tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, etc., and monohydroxy monoacrylates or monohydroxy mono(meth)acrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc.

[0158] (Photopolymerizable monomer having a urethane bond) The photopolymerizable monomer can contain a monomer having an ethylenically unsaturated bond and a urethane bond. The monomer includes, for example, polyfunctional urethane acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting with a (meth)acrylate having a hydroxyl group.

[0159] The (meth)acrylates having a hydroxyl group 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, the reaction product of an epoxy group-containing compound and carboxy (meth)acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

[0160] In addition, the polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, and the like.

[0161] The photopolymerizable monomer can be used alone or in combination of two or more.

[0162] The blending amount of the photopolymerizable monomer is preferably 1 to 50% by mass, more preferably 2 to 40 parts by mass, in 100% by mass of the nonvolatile content of the coloring composition. When an appropriate amount is blended, the curability and developability are further improved.

[0163] <Photopolymerization initiator> The photoinitiator is, for example, an acetophenone-based compound such as 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; a benzoin-based compound such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; a benzophenone-based compound such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; a thioxanthone-based compound such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; a triazine-based compound such as 2,4,6-trichloros-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;1. Oxime ester compounds such as 2 - octanedione, 1 - [4 - (phenylthio)phenyl -, 2 - (O - benzoyloxime)], or ethanone, 1 - [9 - ethyl - 6 - (2 - methylbenzoyl)-9H - carbazol - 3 - yl]-, 1 - (O - acetyloxime); 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, ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds, etc. Among these, oxime ester compounds are preferred.;

[0164] The photoinitiator can be used alone or in combination of two or more kinds.;

[0165] The content of the photoinitiator is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass, based on 100 parts by mass of the colorant. When blended in an appropriate amount, the photocurability and developability are further improved.;

[0166] (Oxime ester compounds) The oxime ester compound absorbs ultraviolet rays, causing the cleavage of the N - O bond of the oxime to generate iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, so that a pattern can be formed with a small exposure amount. When the colorant concentration of the colored composition is high, the ultraviolet transmittance of the coating film may be low and the degree of curing of the coating film may be low. However, the oxime ester compound has a high quantum efficiency and is preferably used.;

[0167] The oxime ester compounds include the compounds described in JP-A-2001-233842, the compounds described in JP-A-2000-80068, the compounds described in JP-A-2006-342166, the compounds described in J.C.S. Perkin II (1979, pp. 1653-1660), the compounds described in J.C.S. Perkin II (1979, pp. 156-162), the compounds described in Journal of Photopolymer Science and Technology (1995, pp. 202-232), the compounds described in JP-A-2000-66385, the compounds described in JP-A-2000-80068, the compounds described in JP-T-2004-534797, the compounds described in JP-A-2006-342166, the compounds described in JP-A-2017-19766, the compounds described in Patent No. 6065596, the compounds described in International Publication WO2015 / 152153, the compounds described in International Publication WO2017 / 051680, the compounds described in JP-A-2007-210991, the compounds described in JP-A-2009-179619, the compounds described in JP-A-2010-037223, the compounds described in JP-A-2010-215575, the compounds described in JP-A-2011-020998, the compounds described in International Publication WO2021 / 175855, and the like.

[0168] Oxime ester compounds include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. Commercially available oxime compounds include IRGACURE - OXEO1, IRGACURE - OXEO2, IRGACURE - OXEO3, IRGACURE - OXEO4 (manufactured by BASF Japan Ltd.), TR - PBG - 304, TR - PBG - 305, TR - PBG - 3057, TR - PBG - 345, TR - PBG - 358 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka Optomer N - 1919, Adeka Arcles NCI - 730, NCI - 831, NCI - 930 (manufactured by ADEKA Corporation). Further, it is preferable to use an oxime compound that is a compound without coloring properties, has high transparency, and is less likely to discolor other components.

[0169] Specifically, when classified by the skeletons contained in the compound, there are a carbazole skeleton, a fluorene skeleton, a diphenyl skeleton, and a dioxime type having two oxime ester groups. Further, as a specific structure contained in the compound, those having a hydroxyl group, a nitro group, a carbonyl group, a fluorinated carbon group, or benzofuran are preferably used.

[0170] Among these, an oxime ester - type photopolymerization initiator having a carbazole structure, an oxime ester - type photopolymerization initiator having a diphenyl skeleton, and an oxime ester - type photopolymerization initiator having two oxime ester groups (including those having a carbazole skeleton) are preferable, and an oxime ester - type photopolymerization initiator having a carbazole structure is most preferable.

[0171] The content of the photoinitiator is preferably 0.1 to 20 parts by mass, more preferably 0.2 to 10 parts by mass, per 100 parts by mass of the nonvolatile content of the colorable composition. When blended in an appropriate amount, the photocurability and the resistance to the developer are improved, and the surface state is improved.

[0172] <Sensitizer> Furthermore, the colorable composition for a color filter of the present invention may contain a sensitizer. Examples of the sensitizer include chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, polymethine dyes such as cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyllin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0173] Among the above sensitizers, the sensitizers that can be particularly preferably sensitized include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, etc. are used.

[0174] More specifically, the sensitizers described in Noboru Okawara et al. (eds.), "Dye Handbook" (1986, Kodansha), Noboru Okawara et al. (eds.), "Chemistry of Functional Dyes" (1981, CMC), Chuichiro Ikemori et al. (eds.), and "Special Functional Materials" (1986, CMC) are included, but not limited to these. In addition, other sensitizers that exhibit absorption for light from ultraviolet to near-infrared regions can also be contained.

[0175] The sensitizer can be used alone or in combination of two or more.

[0176] The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator. When contained in an appropriate amount, the curability and developability are further improved.

[0177] <Thiol-based chain transfer agent> The colorant composition for a color filter of the present invention preferably contains a thiol-based chain transfer agent as a chain transfer agent. By using a thiol together with a photopolymerization initiator, in the radical polymerization process after light irradiation, a thiyl radical that acts as a chain transfer agent and is less susceptible to polymerization inhibition by oxygen is generated, so that the resulting colorant composition has high sensitivity.

[0178] Also, polyfunctional aliphatic thiols in which a thiol group is bonded to an aliphatic group such as methylene or ethylene group having two or more thiol groups are preferred. More preferably, it is a polyfunctional aliphatic thiol having four or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and it is possible to cure from the surface to the vicinity of the substrate in the pattern.

[0179] Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. Preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate are mentioned.

[0180] The thiol-based chain transfer agent can be used alone or in combination of two or more.

[0181] The content of the thiol-based chain transfer agent is preferably 0.1 to 10% by mass, more preferably 0.1 to 3% by mass, in 100% by mass of the non-volatile content of the coloring composition. When contained in an appropriate amount, the photosensitivity and taper shape are improved, and wrinkles are less likely to occur on the film surface.

[0182] <Polymerization inhibitor> The coloring composition for a color filter of the present invention can contain a polymerization inhibitor. Thereby, since the photosensitivity due to the diffracted light of the mask can be suppressed during the exposure of the photolithography method, it becomes easier to obtain a pattern having a desired shape.

[0183] Examples of the polymerization inhibitor 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; alkylresorcinol compounds such as 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide, triphenylphosphine oxide; phosphite compounds such as triphenylphosphite, trisnonylphenylphosphite; pyrogallol, phloroglucin, and the like.

[0184] The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass per 100 parts by mass of the nonvolatile content of the coloring composition. In this range, the effect of the polymerization inhibitor becomes significant, and the linearity of the taper, the wrinkles of the coating film, the pattern resolution, etc. become good.

[0185] <Ultraviolet absorber> The colorant composition for a color filter 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 thereof include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds.

[0186] The content of the ultraviolet absorber is preferably 5 to 70% by mass in a total of 100% by mass of the photopolymerization initiator and the ultraviolet absorber. When contained in an appropriate amount, the developability after development is further improved.

[0187] Further, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass in 100% by mass of the non-volatile content of the photosensitive colorant composition. When contained in an appropriate amount, the adhesion between the substrate and the film is further improved, and good developability is obtained.

[0188] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 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, a mixture of 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, a mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, the reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-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-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate. Other oligomer-type and polymer-type compounds having a benzotriazole structure can also be used.

[0189] 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-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, etc. Other oligomer-type and polymer-type compounds having a triazine structure can also be used.

[0190] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2,2'-dihydroxy-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, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc. Other oligomer-type and polymer-type compounds having a benzophenone structure can also be used.

[0191] Examples of the salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc. In addition, oligomer-type and polymer-type compounds having a salicylic acid ester structure can also be used.

[0192] <Antioxidant> The colored composition for a color filter of the present invention can contain an antioxidant. The antioxidant can prevent the photoinitiator and thermosetting compound contained in the colored composition from being oxidized and yellowed by the heat treatment during thermosetting or ITO annealing, thereby improving the transmittance of the coating film. In particular, when the colorant concentration of the colored composition is high, since the amount of the crosslinking component in the coating film is small, a phenomenon in which yellowing during the heat treatment becomes stronger due to measures such as using a highly sensitive crosslinking component or increasing the amount of the photoinitiator is observed. 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.

[0193] Examples of the antioxidant include compounds of the hindered phenol type, hindered amine type, phosphorus type, sulfur type, and hydroxylamine type. In this specification, the antioxidant is preferably a compound that does not contain a halogen atom.

[0194] Among these, from the viewpoint of achieving both the transmittance and sensitivity of the coating film, hindered phenol type antioxidants, hindered amine type antioxidants, phosphorus type antioxidants, and sulfur type antioxidants are preferred.

[0195] The antioxidant can be used alone or in combination of two or more.

[0196] Also, when the content of the antioxidant is 0.5 to 5.0% by mass in 100% by mass of the solid content of the colored composition, it is more preferable because the transmittance, spectral characteristics, and sensitivity are good.

[0197] <Levelling agent> In the colorant composition for a color filter of the present invention, it is preferable to add a leveling agent for the purpose of improving the coatability of the composition on a transparent substrate and the drying property of the colored film. As the leveling agent, various surfactants such as silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used.

[0198] Examples of the silicone-based surfactant include a linear polymer composed of a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.

[0199] 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 manufactured by BYK Chemie GmbH; FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Toray Dow Corning Co., Ltd.; 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 manufactured by Shin-Etsu Chemical Co., Ltd. etc. can be mentioned.

[0200] Examples of the fluorine-based surfactant include a surfactant or a leveling agent having a fluorocarbon chain.

[0201] More specifically, Surfron S-242, S-243, S-420, S-611, S-651, S-386 manufactured by 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 manufactured by DIC Corporation; FC-4430, FC-4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; Fugennto 602A manufactured by Neos Co., Ltd. etc. can be mentioned.

[0202] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrylphenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, 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 sorbitol tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkylalkanolamide, alkylimidazoline, and the like.

[0203] More specifically, examples include 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, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Lathamul PD-420, PD-430, PD-430S, PD450, Leodol 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-L106, 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), Amite 102, 105, 105A, 302, 320, Aminon PK-02S, L-02, Homogenol L-95, ADEKA Corporation's Adeka Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, Kyoeisha Chemical Co., Ltd.'s (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95, etc.

[0204] Examples of cationic surfactants include alkylamine salts, and alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0205] More specifically, examples include Kao Corporation's Acetamine 24, Kotamine 24P, 60W, 86P Conc, etc.

[0206] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyl diphenyl ether disulfonate, lauryl sulfate monoethanolamine, lauryl sulfate triethanolamine, ammonium lauryl sulfate, stearic acid monoethanolamine, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphates, and the like.

[0207] More specifically, examples include Ftergent 100 and 150 manufactured by Neos Co., Ltd., Adekahoop YES-25, Adekacol TS-230E, PS-440E, EC-8600 manufactured by ADEKA Corporation, and the like.

[0208] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyl dimethylaminoacetic acid betaine, and alkylamine oxides such as lauryl dimethylamine oxide.

[0209] More specifically, examples include Amphitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N manufactured by Kao Corporation, and the like.

[0210] When the coloring composition of the present invention contains a surfactant, the addition amount of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on the total solid content of the composition of the present invention. By being within this range, the balance of the coatability, pattern adhesion, and transmittance of the coloring composition becomes good. The coloring composition of the present invention may contain only one type of surfactant or may contain two or more types of surfactants. When two or more types are contained, it is preferable that the total amount thereof is within the above range.

[0211] <Storage Stabilizer> In the colorant composition for a color filter of the present invention, a storage stabilizer can be contained in order to stabilize the viscosity of the colorant composition over time. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine, and phosphites. 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).

[0212] <Adhesion improver> In the colorant composition for a color filter of the present invention, an adhesion improver such as a silane coupling agent can be contained in order to enhance the adhesion to a substrate. By improving the adhesion with the adhesion improver, the reproducibility of fine lines becomes good and the resolution is improved.

[0213] Examples of the adhesion promoter include silane coupling agents such as vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; aminosilanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercaptans such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureides such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatopropyltriethoxysilane.

[0214] The adhesion promoter 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 coloring composition. Using it within this range is more preferable because the effect is enhanced and the balance of adhesion, resolution, and sensitivity is good.

[0215] <Method for producing the coloring composition> The colored composition for color filters of the present invention can be produced by finely dispersing a colorant in a colorant carrier such as a dispersant and a binder resin and / or a solvent, preferably together with a dispersion aid (dye derivative or surfactant), using various dispersion means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor (colorant dispersion). At this time, two or more colorants etc. may be dispersed in the colorant carrier simultaneously, or those separately dispersed in the colorant carrier may be mixed. When the solubility of the colorant such as a dye is high, specifically, when the solubility in the solvent to be used is high and dissolution is confirmed by stirring and no foreign matter is observed, it is not necessary to produce by finely dispersing as described above.

[0216] Also, when used as a photosensitive colored composition (resist material) for color filters, it can be prepared as a solvent-developable or alkali-developable colored composition. The solvent-developable or alkali-developable colored composition can be prepared by mixing the above-mentioned colorant dispersion, a photopolymerizable monomer and / or a photoinitiator, and, if necessary, a solvent, other dispersion aids, and additives etc. The photoinitiator may be added at the stage of preparing the colored composition, or may be added later to the prepared colored composition.

[0217] <Removal of Coarse Particles> The colored composition for color filters of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more and mixed dust by means such as centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or a membrane filter. Thus, it is preferable that the colored composition substantially does not contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

[0218] <Water Content in the Colored Composition> The colored composition for color filters of the present invention preferably has a water content of 0.1 to 2.0 mass% with respect to the whole colored composition.

[0219] When the coloring composition has a water content within the above range, it exhibits excellent dispersion stability and sensitivity even after storage over time.

[0220] The water content in the coloring composition is preferably 1.8% by mass or less, more preferably 1.6% by mass or less. With such a sufficiently small amount of water in this range, problems with dispersion stability and sensitivity are less likely to occur even after storage over time.

[0221] The method for controlling the water content is not particularly limited, and known methods can be used. For example, methods such as manufacturing the coloring composition while blowing in dry inert gas, or adding molecular sieves for dehydration after manufacturing can be mentioned. Among them, the method of manufacturing while blowing in dry inert gas is preferred.

[0222] The water content can be measured by known methods such as the Karl Fischer method.

[0223] <Specific metal atoms in the coloring composition> In the coloring composition for a color filter of the present invention, there may be a metal component containing a small amount of Li, Na, K, Mg, Ca, Fe, and Cr (hereinafter also referred to as specific metal atoms) in addition to the constituent components of the pigment. When there is a large amount of the metal component containing these specific metal atoms, the storage stability may be inhibited, the heat resistance may decrease, or the sensitivity may decrease when prepared in the form of a photosensitive coloring composition. In addition, a color filter prepared using a coloring composition in which there is a large amount of the metal component containing such specific metal atoms may generate foreign substances, and as a result, the transmittance is likely to decrease. The total content of the specific metal atoms in the metal component contained in the coloring composition for a color filter of the present invention is preferably 1 to 500 mass ppm with respect to the entire coloring composition.

[0224] The total amount of specific metal atoms contained in the coloring composition for a color filter of the present invention is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less, based on the entire coloring composition. The lower limit of the total amount of specific metal atoms is not particularly limited, but is preferably 1 mass ppm or more, more preferably 5 mass ppm or more, based on the entire coloring composition. Within the above range, a coloring composition can be obtained that can suppress costs, has excellent storage stability, and forms a color filter with less generation of foreign matter and less reduction in transmittance.

[0225] The content of each specific metal atom contained in the coloring composition for a color filter of the present invention is preferably 100 mass ppm or less, more preferably 50 mass ppm or less, respectively, based on the entire coloring composition.

[0226] In addition, when a metal atom such as Ni, Zn, Cu, Al, Fe, or Co is contained in a part of the pigment structure, these metal atoms that do not constitute a part of the pigment structure may be present. It is better that there are also fewer such metal atoms, and they can be removed in the same manner as specific metal atoms by the following method. Furthermore, those mixed in by materials (such as catalysts) used in the manufacturing processes of various raw materials of the coloring composition, such as Mn, Cs, Ti, Co, Si, Pd, etc., are preferably present at low concentrations.

[0227] As methods for removing metal atoms mixed in from various raw materials contained in the coloring composition or from the apparatus during the manufacturing process, methods such as washing with water according to JP-A-2010-83997, JP-A-2018-36521, JP-A-7-198928, JP-A-8-333521, JP-A-2009-7432, etc., and methods for removing magnetic foreign matter using a magnet described in JP-A-2011-48736 can be mentioned, and these can be used alone or in combination as appropriate.

[0228] The content of specific metal atoms can be measured by inductively coupled plasma optical emission spectrometry (ICP).

[0229] <Amount of toluene in the coloring composition> The colorant composition for a color filter of the present invention may contain toluene. When it contains toluene, the content of toluene is preferably 0.1 to 10 mass ppm. The upper limit of the toluene content is preferably 9 mass ppm or less, more preferably 8 mass ppm or less, and still more preferably 7 mass ppm or less. The lower limit is preferably 0.2 mass ppm or more, more preferably 0.3 mass ppm or more, and still more preferably 0.4 mass ppm or more.

[0230] <Color filter> Next, the color filter of the present invention will be described. The color filter of the present invention includes a red filter segment, a green filter segment, and a blue filter segment. Further, the color filter may further include a magenta filter segment, a cyan filter segment, and a yellow filter segment. At least one of the red filter segment and the yellow filter segment of the color filter of the present invention is formed from the colorant composition for a color filter of the present invention. In particular, it is preferable that the red filter segment is formed from the colorant composition for a color filter of the present invention.

[0231] (Method for manufacturing a color filter) For the color filter, it is preferable to first form a black matrix on a substrate and then form filter segments. Note that a thin film transistor (TFT) can be formed on the substrate in advance and then the black matrix can be formed. Examples of the substrate include a substrate made of a material such as glass, resin, or silicon. An organic light-emitting layer may be formed on these substrates. Further, an imaging element such as a CCD or a CMOS may be formed on the substrate. Further, a undercoat layer may be provided on the substrate as necessary for improving adhesion to an upper layer, preventing diffusion of substances, and planarizing the substrate surface. Examples of the black matrix include an inorganic film such as chromium, a multilayer film of chromium / chromium oxide, titanium nitride, or a resin film in which a light-shielding agent is dispersed.

[0232] The formation of the filter segment can be produced by, for example, printing method, electrodeposition method, transfer method, inkjet method, photolithography method, dry etching method, etc.

[0233] The printing method can form a pattern only by repeating the printing and drying of the coloring composition prepared as printing ink. Therefore, as a method for manufacturing a color filter, it is low-cost and excellent in mass productivity. Furthermore, due to the development of printing technology, it is possible to print fine patterns having high dimensional accuracy and smoothness. In order to perform printing, it is preferable to have a composition such that the ink does not dry or solidify on the printing plate or on the blanket. Also, the control of the fluidity of the ink on the printing machine is important, and the viscosity of the ink can be adjusted with a dispersant or an extender pigment.

[0234] The electrodeposition method manufactures a color filter by using a transparent conductive film formed on a transparent substrate and electrodepositing filter segments of each color on the transparent conductive film by electrophoresis of colloidal particles. Also, in the transfer method, a filter segment is formed on the peeling surface of a peelable sheet. Then, this filter segment is transferred onto a transparent substrate for manufacturing.

[0235] The photolithography method involves coating a layer formed by applying the coloring composition of the present invention on a substrate, drying (pre-baking) it if necessary, then exposing it in a pattern through a mask (exposure step), removing the unexposed portion by alkali development (development step), and then heat-treating the pattern (post-baking step) if necessary.

[0236] 〔Exposure step〕 In the exposure process, the layer formed by coating is exposed to a specific pattern through a mask using an exposure apparatus such as a stepper. As a result, the exposed portion can be cured. Examples of the active energy ray used for exposure include ultraviolet rays such as g-line (wavelength 436 nm), h-line (wavelength 405 nm), and i-line (wavelength 365 nm). Also, light with a wavelength of 300 nm or less can be used. Examples of light with a wavelength of 300 nm or less include KrF line (wavelength 248 nm) and ArF (wavelength 193 nm). Also, at the time of exposure, the exposure may be performed by continuously irradiating light, or the exposure may be performed by repeating the irradiation and pause of light in a short cycle (for example, at the millisecond level or less) (pulse exposure).

[0237] 〔Development process〕 Next, by performing an alkali development process, the layer of the unexposed portion is eluted into an aqueous alkali solution, and only the cured portion remains to obtain a patterned film. Examples of the alkali developer include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkali developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkali developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, roughness and peeling of the pattern are suppressed, and the residual film rate after development is improved. Examples of the development method include a dip method, a spray method, and a paddle method. The development temperature is preferably 15 to 40°C. After alkali development, it is preferably washed with pure water.

[0238] 〔Post-bake process〕 After development, heat treatment (post-bake) can be performed as necessary. The post-bake improves the resistance of the film. 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.

[0239] In the dry etching method, for example, a layer formed by coating the coloring 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 the dry etching method, the method described in JP-A-2013-064993 can be referred to.

[0240] The color filter of the present invention is bonded to a counter substrate using a sealant, liquid crystal is injected from an injection port provided in the seal portion, and then the injection port is sealed. If necessary, a polarizing film or a retardation film is bonded to the outside of the substrate to manufacture a color liquid crystal display device. This color liquid crystal display device can be used in a liquid crystal display mode for colorization using a color filter such as Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertical Alignment (VA), Optically Compensated Bend (OCB), etc.

[0241] The color filter of the present invention can be used in applications such as solid-state imaging devices, organic EL display devices, quantum dot display devices, electronic paper, and head-mounted displays in addition to liquid crystal display devices.

[0242] <Liquid Crystal Display Device> A liquid crystal display device including the color filter of the present invention will be described. The liquid crystal display device of the present invention includes the color filter of the present invention and a light source. Examples of the light source include a cold cathode tube (CCFL) and a white LED. In the present invention, it is preferable to use a white LED in terms of the expansion of the red reproduction region. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 including the color filter of the present invention. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 disposed opposite to each other with a gap therebetween, and a liquid crystal LC is encapsulated therebetween.

[0243] The liquid crystal LC is aligned according to driving modes such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane switching), VA (Vertical Alignment), and OCB (Optically Compensated Birefringence). On the inner surface of the first transparent substrate 11, a TFT (Thin Film Transistor) array 12 is formed, and on top of that, a transparent electrode layer 13 made of, for example, ITO is formed. An alignment layer 14 is provided on the transparent electrode layer 13. Further, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0244] On the other hand, on the inner surface of the second transparent substrate 21, the color filter 22 of the present invention is formed. The red, green, and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0245] A transparent protective film (not shown) is formed as needed to cover the color filter 22, and on top of that, a transparent electrode layer 23 made of, for example, ITO is formed, and an alignment layer 24 is provided to cover the transparent electrode layer 23.

[0246] Further, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

[0247] As white LED light sources, there are those in which a fluorescent filter is formed on the surface of a blue LED, and those in which a phosphor is contained in the resin package of a blue LED. They have a wavelength (λ3) at which the emission intensity is maximized within the range of 430 nm to 485 nm, a wavelength (λ4) at which the emission intensity is maximized within the range of 530 nm to 580 nm, and a wavelength (λ5) at which the emission intensity is maximized within the range of 600 nm to 650 nm. Also, a white LED light source (LED1) having spectral characteristics such that the ratio (I4 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio (I5 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less, or a white LED light source (LED2) having spectral characteristics such that it has a wavelength (λ1) at which the emission intensity is maximum within the range of 430 nm to 485 nm, a peak wavelength (λ2) of the second emission intensity within the range of 530 nm to 580 nm, and the ratio (I2 / I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 is 0.2 or more and 0.7 or less is preferred.

[0248] Specific examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.).

[0249] Specific examples of LED2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D (manufactured by Nichia Chemical Industries, Ltd.).

[0250] <Solid-state imaging device> The solid-state imaging device of the present invention has a configuration including the color filter of the present invention, and is not particularly limited as long as it functions as a solid-state imaging device. For example, the following configurations can be mentioned. On a substrate, there are a plurality of photodiodes constituting a light-receiving area of a solid-state imaging device (such as a CCD sensor, a CMOS sensor, an organic CMOS sensor, etc.) and transfer electrodes made of polysilicon or the like. On the photodiodes and the transfer electrodes, there is a light-shielding film made of tungsten or the like with only the light-receiving portion of the photodiodes opened. On the light-shielding film, there is a device protection film made of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiodes. On the device protection film, there is a configuration having the color filter of the present invention. Furthermore, a configuration having a condensing means (for example, a microlens or the like. The same applies hereinafter) on the device protection layer and under the color filter (the side closer to the substrate), or a configuration having a condensing means on the color filter may be employed. The imaging device provided with the solid-state imaging device of the present invention can be used in various applications such as, for example, a digital camera, an electronic device having an imaging function (such as a smartphone, a tablet terminal, etc.), an in-vehicle camera, a surveillance camera, and an optical sensor.

Example

[0251] Hereinafter, the present invention will be described based on examples, but the present invention is not limited thereto. In the examples, “parts” and “%” represent “parts by mass” and “mass%”, respectively. The weight average molecular weight (Mw) of the resin is as follows.

[0252] (Weight average molecular weight (Mw) of carboxylic acid resin type dispersant and binder resin) The weight average molecular weight (Mw) of the carboxylic acid resin type dispersant and the binder resin is the weight average molecular weight (Mw) in terms of polystyrene measured using a TSKgel column (manufactured by Tosoh Corporation) with an RI detector equipped in a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) using THF as the developing solvent.

[0253] (Acid value of carboxylic acid resin type dispersant and binder resin) To 0.5 - 1 g of a carboxylic acid resin type dispersant solution and a binder resin solution, 80 ml of acetone and 10 ml of water were added, stirred, and uniformly dissolved. Using a 0.1 mol / L aqueous KOH solution as the titrant, titration was performed using an automatic titrator (model "COM - 555", manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value (mgKOH / g) was measured. Then, from the acid value of the resin solution and the solid content concentration of the resin solution, the acid value per solid content of the resin was calculated.

[0254] (Basic resin type dispersant: average molecular weight of acrylic block copolymer) For the basic resin type dispersant: acrylic block copolymer, the number average molecular weight (Mn) and weight average molecular weight (Mw) were measured using HLC - 8320GPC (manufactured by Tosoh Corporation) as the apparatus, SUPER - AW3000 as the column, and a solution of 30 mM triethylamine and 10 mM LiBr in N,N - dimethylformamide as the eluent. The values are the number average molecular weight (Mn) and weight average molecular weight (Mw) in terms of polystyrene conversion.

[0255] (Basic resin type dispersant: amine value of acrylic block copolymer) For the basic resin type dispersant: acrylic block copolymer, the amine value is the value obtained by converting the measured total amine value (mgKOH / g) to solid content in accordance with the method of ASTM D 2074.

[0256] <Production of quinophthalone - based dye derivative (B1)> (Quinophthalone - based dye derivative (B1 - 1)) 30 parts of C.I. Pigment Yellow 138 (manufactured by BASF, "Paliotol Yellow K0960 - HD"), a quinophthalone compound, was dissolved in 300 parts of 101% sulfuric acid, stirred at 70 °C for 8 hours to carry out a sulfonation reaction. The end point of the reaction was determined as the point where no change in the spectral spectrum of the sulfuric acid solution was observed. Next, this reaction solution was poured into 3000 parts of ice water, the precipitate was filtered off, washed with water, and dried at 80 °C to obtain a quinophthalone - based dye derivative (B1 - 1) represented by the following formula (1).

[0257] Formula (1) [Chemical formula]

[0258] (Quinophthalone-based dye derivative (B1-2)) According to the synthesis method described in Japanese Patent No. 4585781, the quinophthalone-based dye derivative (B1-2) represented by the following formula (2) was obtained.

[0259] Formula (2) [Chemical formula]

[0260] (Quinophthalone-based dye derivative (B1-3)) 10 g of the quinophthalone-based dye derivative (B1-1) was added to 500 parts of water, stirred at 25°C for 2 hours, and redispersed. Then, 4.8 parts of copper(II) sulfate pentahydrate was gradually added to this solution, and the reaction was carried out at 60°C for 2 hours. The reaction product was filtered off, washed with water, and dried at 80°C to obtain the quinophthalone-based dye derivative (B1-3) represented by the following formula (3).

[0261] Formula (3) [Chemical formula]

[0262] (Quinophthalone-based dye derivative (B1-4)) The quinophthalone-based dye derivative (B1-4) represented by the following formula (4) was obtained in the same manner as the quinophthalone-based dye derivative (B1-3), except that 5.2 parts of iron(III) chloride hexahydrate was used instead of the copper(II) sulfate pentahydrate used in the production of the quinophthalone-based dye derivative (B1-3).

[0263] Formula (4) [Chemical formula]

[0264] (Quinophthalone-based dye derivative (B1-5)) A quinophthalone-based dye derivative (B1-5) represented by the following formula (5) was obtained in the same manner as the quinophthalone-based dye derivative (B1-3), except that 3.4 parts of calcium acetate monohydrate was used instead of copper(II) sulfate pentahydrate used in the production of the quinophthalone-based dye derivative (B1-3).

[0265] Formula (5)

Chemical formula

[0266] (Quinophthalone-based dye derivative (B1-6)) A quinophthalone-based dye derivative (B1-6) represented by the following formula (6) was obtained in the same manner as the quinophthalone-based dye derivative (B1-3), except that 4.3 parts of zinc acetate dihydrate was used instead of copper(II) sulfate pentahydrate used in the production of the quinophthalone-based dye derivative (B1-3).

[0267] Formula (6)

Chemical formula

[0268] (Quinophthalone-based dye derivative (B1-7)) A quinophthalone-based dye derivative (B1-7) represented by the following formula (7) was obtained in the same manner as the quinophthalone-based dye derivative (B1-3), except that 3.9 parts of magnesium chloride (II) hexahydrate was used instead of copper(II) sulfate pentahydrate used in the production of the quinophthalone-based dye derivative (B1-3).

[0269] Formula (7)

Chemical formula

[0270] <Production of quinoline-based dye derivative (B2)> (Quinoline-based dye derivative (B2-1)) 45 parts of C.I. Pigment Yellow 138 (Paliotol Yellow K0960-HD manufactured by BASF), which is a quinophthalone compound, was dissolved in 450 parts of 98% sulfuric acid, and stirred at 70 °C for 1 hour to carry out a sulfonation reaction. The end point of the reaction was determined as the point where no change in the spectral spectrum of the sulfuric acid solution was observed. Next, this reaction solution was poured into 5000 parts of ice water, the precipitate was filtered off, washed with 2000 parts of 0.1% hydrochloric acid, and further washed with 2000 parts of purified water to obtain a paste of the sulfonated product of C.I. Pigment Yellow 138. The obtained sulfonated product paste was redispersed in 5000 parts of water (the pH of the redispersed slurry was 2.3), and 25% sodium hydroxide solution was added while stirring to adjust the pH to 11.5. During the pH adjustment, the reaction solution changed from a yellow slurry state to a red solution state. Fine pH adjustment was performed every 5 minutes for 1 hour. Further, it was heated to 60 °C at pH 11.5 and stirred for 3 hours. Next, 98% sulfuric acid was added to this reaction solution while stirring to adjust the pH to below 1. During the pH adjustment, a precipitate was generated, which was filtered off, washed with a large amount of water, and then dried at 80 °C to obtain a quinoline-based dye derivative (B2-1) represented by the following formula (8).

[0271] Formula (8)

Chemical formula

[0272] (Quinoline-based dye derivative (B2-2)) According to the synthesis method described in JP-A-2011-102945, a quinoline-based dye derivative (B2-2) represented by the following formula (9) was obtained.

[0273] Formula (9)

Chemical formula

[0274] (Quinoline-based dye derivative (B2-3)) 10 g of the quinoline-based dye derivative (B2-1) was added to 500 parts of water, stirred at 25 °C for 2 hours, and redispersed. Next, 4.8 parts of copper(II) sulfate pentahydrate was gradually added to this solution, and the mixture was reacted at 60 °C for 2 hours. The reaction product was filtered off, washed with water, and dried at 80 °C to obtain a quinoline-based dye derivative (B2-3) represented by the following formula (10).

[0275] Formula (10)

Chemical formula

[0276] (Quinoline-based dye derivative (B2-4)) A quinoline-based dye derivative (B2-4) represented by the following formula (11) was obtained in the same manner as the quinoline-based dye derivative (B2-3), except that 5.2 parts of iron(III) chloride hexahydrate was used instead of copper(II) sulfate pentahydrate used in the production of the quinoline-based dye derivative (B2-3).

[0277] Formula (11)

Chemical formula

[0278] (Quinoline-based dye derivative (B2-5)) A quinoline-based dye derivative (B2-5) represented by the following formula (12) was obtained in the same manner as the quinoline-based dye derivative (B2-3), except that 3.4 parts of calcium acetate monohydrate was used instead of copper(II) sulfate pentahydrate used in the production of the quinoline-based dye derivative (B2-3).

[0279] Formula (12)

Chemical formula

[0280] (Quinoline-based dye derivative (B2-6)) A quinoline-based dye derivative (B2-6) represented by the following formula (13) was obtained in the same manner as the quinoline-based dye derivative (B2-3), except that 4.3 parts of zinc acetate dihydrate was used instead of copper(II) sulfate pentahydrate used in the production of the quinoline-based dye derivative (B2-3).

[0281] Formula (13) [Chemical formula]

[0282] (Quinoline-based dye derivative (B2-7)) A quinoline-based dye derivative (B2-7) represented by the following formula (14) was obtained in the same manner as the previous quinoline-based dye derivative (B2-3), except that 3.9 parts of magnesium chloride(II) hexahydrate was used instead of copper(II) sulfate pentahydrate used in the production of the quinoline-based dye derivative (B2-3).

[0283] Formula (14) [Chemical formula]

[0284] [Production of quinoline-based dye derivative (B3)] (Quinoline-based dye derivative (B3-1)) 45 parts of C.I. Pigment Yellow 138 (Paliotol Yellow K0960-HD manufactured by BASF), which is a quinophthalone compound, was dissolved in 450 parts of 98% sulfuric acid, and stirred at 80 °C for 3 hours to carry out a sulfonation reaction. The end point of the reaction was determined as the point where no change in the spectral spectrum of the sulfuric acid solution was observed. Next, this reaction solution was poured into 5000 parts of ice water, the precipitate was filtered off, washed with 2000 parts of 0.1% hydrochloric acid, and further washed with 2000 parts of purified water to obtain a paste of the sulfonated product of C.I. Pigment Yellow 138. The obtained sulfonated product paste was redispersed in 5000 parts of water (the pH of the redispersed slurry was 2.3), and 25% sodium hydroxide solution was added while stirring to adjust the pH to 12.5. During the pH adjustment, the reaction solution changed from a yellow slurry state to a red solution state. Fine pH adjustment was carried out every 5 minutes for 2 hours. Further, it was heated to 80 °C at pH 12.5 and stirred for 3 hours. Next, 98% sulfuric acid was added to this reaction solution while stirring to adjust the pH to below 1. During the pH adjustment, a precipitate was generated, which was filtered off, washed with a large amount of water, and then dried at 80 °C to obtain a quinoline-based dye derivative (B3-1) represented by the following formula (15).

[0285] Formula (15)

Chemical formula

[0286] (Quinoline-based dye derivative (B3-2)) According to the synthesis method described in JP-A No. 2011-102945, a quinoline-based dye derivative (B3-2) represented by the following formula (16) was obtained.

[0287] Formula (16)

Chemical formula

[0288] (Quinoline-based dye derivative (B3-3)) 10 g of the quinoline-based dye derivative (B3-1) was added to 500 parts of water and stirred at 25 °C for 2 hours for redispersion. Next, 4.8 parts of copper(II) sulfate pentahydrate was gradually added to this solution and reacted at 60 °C for 2 hours. The reaction product was filtered off, washed with water, and dried at 80 °C to obtain a quinoline-based dye derivative (B3-3) represented by the following formula (17).

[0289] Formula (17)

Chemical formula

[0290] (Quinoline-based dye derivative (B3-4)) A quinoline-based dye derivative (B3-4) represented by the following formula (18) was obtained in the same manner as the quinoline-based dye derivative (B3-3), except that 5.2 parts of iron(III) chloride hexahydrate was used instead of the copper(II) sulfate pentahydrate used in the production of the quinoline-based dye derivative (B3-3).

[0291] Formula (18)

Chemical formula

[0292] (Quinoline-based dye derivative (B3-5)) A quinoline-based dye derivative (B3-5) represented by the following formula (19) was obtained in the same manner as the quinoline-based dye derivative (B3-3), except that 3.4 parts of calcium acetate monohydrate was used instead of the copper(II) sulfate pentahydrate used in the production of the quinoline-based dye derivative (B3-3).

[0293] Formula (19)

Chemical formula

[0294] (Quinoline-based dye derivative (B3-6)) A quinoline-based dye derivative (B3-6) represented by the following formula (20) was obtained in the same manner as the quinoline-based dye derivative (B3-3), except that 4.3 parts of zinc acetate dihydrate was used instead of the copper(II) sulfate pentahydrate used in the production of the quinoline-based dye derivative (B3-3).

[0295] Formula (20)

Chemical formula

[0296] (Quinoline-based dye derivative (B3-7)) A quinoline-based dye derivative (B3-7) represented by the following formula (21) was obtained in the same manner as the quinoline-based dye derivative (B3-3), except that 3.9 parts of magnesium chloride(II) hexahydrate was used instead of the copper(II) sulfate pentahydrate used in the production of the quinoline-based dye derivative (B3-3).

[0297] Formula (21)

Chemical formula

[0298] [Synthesis Example 6] <Synthesis of Dye Derivative (B-6)>[ 30 parts of C.I. Pigment Red 272 (BASF's "Irgazin RED K3800") was charged at room temperature into 300 parts of 102% fuming sulfuric acid. After stirring at room temperature for 3 hours, it was added dropwise to 1500 parts of cold methyl ethyl ketone over 30 minutes. The precipitate was filtered, washed with 3000 parts of ice-cold methyl ethyl ketone, and dried at 80 °C to obtain 10.2 parts of the dye derivative (B-6). Thus, the dye derivative (B-6) represented by the following structure was produced.

[0299] Dye Derivative (B-6)

Chemical formula

[0300] [Synthesis Example 7] <Synthesis of Dye Derivative (B-7)> With reference to Production Example 6 of Patent No. 4983061, a dye derivative (B-7) represented by the following structure was produced.

[0301] Dye Derivative (B-7)

Chemical Structure

[0302] <Production of Red Pigment (A-1)> A mixture of 300 parts of an anthraquinone-based red pigment (C.I. Pigment Red 177, Cinilex Red SR3C manufactured by CINIC), 1500 parts of sodium chloride, and 150 parts of diethylene glycol was kneaded at 60°C for 6 hours using a 1-gallon stainless-steel kneader (manufactured by Inoue Seisakusho). Next, this kneaded material was put into 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C for a whole day and night to obtain 290 parts of red pigment (A-1).

[0303] <Production of Red Pigment (A-2)> A mixture of 300 parts of a diketopyrrolopyrrole-based red pigment (C.I. Pigment Red 254, Irgazin RED L3630 manufactured by BASF), 1500 parts of sodium chloride, and 150 parts of diethylene glycol was kneaded at 60°C for 6 hours using a 1-gallon stainless-steel kneader (manufactured by Inoue Seisakusho). Next, this kneaded material was put into 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C for a whole day and night to obtain 290 parts of red pigment (A-2).

[0304] <Production of Red Pigment (A-3)> A mixture of 300 parts of a diketopyrrolopyrrole-based red pigment (C.I. Pigment Red 291, CinilexDPPMT-CF manufactured by CINIC), 1500 parts of sodium chloride, and 150 parts of diethylene glycol was kneaded at 60 °C for 6 hours using a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho). Next, this kneaded product was put into 5 liters of warm water and stirred for 1 hour while heating to 70 °C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80 °C for a whole day and night to obtain 291 parts of a red pigment (A-3).

[0305] <Production of Red Pigment (A-4)> A mixture of 300 parts of an azo-based red pigment (C.I. Pigment Red 242, Novoperm Scarlet 4RF manufactured by Clariant), 1500 parts of sodium chloride, and 150 parts of diethylene glycol was kneaded at 60 °C for 6 hours using a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho). Next, this kneaded product was put into 5 liters of warm water and stirred for 1 hour while heating to 70 °C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80 °C for a whole day and night to obtain 291 parts of a red pigment (A-4).

[0306] <Production of Binder Resin (C)> (Binder Resin (C1-1) Solution) 262.0 parts of propylene glycol monomethyl ether acetate (hereinafter, PGMAc) was put into a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, and a stirrer in a reaction vessel, and heated to 120 °C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 49.7 parts of 2-ethylhexyl acrylate (hereinafter, 2-EHA), 99.4 parts of glycidyl methacrylate (hereinafter, GMA), 6.6 parts of dicyclopentanyl methacrylate (hereinafter, DCPMA), and 19.0 parts of t-butylperoxy-2-ethylhexanoate as a polymerization initiator and PGMAc was added dropwise through a dropping tube over 2.5 hours. After the dropping was completed, the mixture was further stirred at 120 °C for 2 hours to obtain a precursor. Then, the inside of the flask was replaced with air, and 50.4 parts of acrylic acid (hereinafter referred to as AA), 0.6 part of triphenylphosphine as a catalyst, and 0.2 part of methylhydroquinone were added, and the reaction was carried out at 110 °C for 10 hours. As a result, a monomer unit (hereinafter referred to as GMA+AA) in which the epoxy group of GMA reacts with the carboxyl group of AA was obtained, and a polymerizable unsaturated group-containing monomer unit (c2) was introduced. Next, 21.3 parts of tetrahydrophthalic anhydride (hereinafter referred to as THPA) was added as a modified compound, and the reaction was carried out at 110 °C for 4 hours. As a result, a part of the hydroxyl group of GMA+AA reacted with THPA. Then, PGMAc was added so that the non-volatile content became 20% by mass, and a binder resin (C1-1) solution containing an alicyclic hydrocarbon-containing monomer unit (c1) and a polymerizable unsaturated group-containing monomer unit (c2) was prepared. The binder resin (C1-1) had an acid value of 38 mgKOH / g, a weight average molecular weight of 12,000, and a composition ratio (mol%) of dicyclopentanyl methacrylate / GMA+AA / GMA+AA+THPA / 2-ethylhexyl acrylate = 3 / 56 / 14 / 27.

[0307] (Binder resin (C1-2) to (C1-6) solutions) The types and amounts of the components were changed so as to obtain the composition ratios (mol%) shown in Table 1, and the binder resins (C1-2) to (C1-6) were synthesized in the same manner as the binder resin (C1-1), and PGMAc was added to make the non-volatile content 20% by mass.

[0308]

Table 1

[0309] MAA+GMA shown in Table 1 represents a polymerizable unsaturated group-containing monomer unit (c2) in which the epoxy group of GMA is added to the carboxyl group of methacrylic acid (hereinafter referred to as MAA) in the precursor. GMA+AA+SHA represents a polymerizable unsaturated group-containing monomer unit (c2) in which a part of the hydroxyl group of GMA+AA reacts with succinic anhydride (hereinafter referred to as SHA).

[0310] (Binder resin (C2-1) solution) Into a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube and a stirrer, 196 parts of cyclohexanone were charged and the temperature was raised to 80 °C. After purging the inside of the reaction vessel with nitrogen, a mixture of 25.1 parts of benzyl methacrylate, 23.0 parts of n-butyl methacrylate, 14.3 parts of 2-hydroxyethyl methacrylate, 13.4 parts of methacrylic acid, 24.1 parts of para-cumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2’-azobisisobutyronitrile was added dropwise over 2 hours from the dropping tube. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of the acrylic resin. After cooling to room temperature, about 2 parts of the resin solution were sampled and heated and dried at 180 °C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized resin solution so that the nonvolatile content became 20% by mass, and a binder resin (C2-1) solution was prepared. The binder resin (C2-1) had an acid value of 87 mgKOH / g, a weight average molecular weight of 25,000, and a composition ratio (mol%) of benzyl methacrylate / methacrylic acid / n-butyl methacrylate / 2-hydroxyethyl methacrylate / para-cumylphenol ethylene oxide-modified acrylate = 22 / 24 / 25 / 17 / 12.

[0311] (Binder resins (C2-2) and (C2-3) solutions) The types and amounts of the components were changed so as to have the composition ratios shown in Table 2, and binder resins (C2-2) and (C2-3) were synthesized. PGMAc was added to make the nonvolatile content 20% by mass.

[0312]

Table 2

[0313] <Method for producing a basic resin type dispersant: acrylic block copolymer> (Production example of acrylic block copolymer (E-1): AB type block polymer) Into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 60 parts of methyl methacrylate, 20 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged. While flowing nitrogen, the mixture was stirred at 50 °C for 1 hour, and the inside of the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 133 parts of methoxypropyl acetate were charged. Under a nitrogen stream, the temperature was raised to 110 °C to initiate the polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled for solid content measurement, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile content. Next, 61 parts of methoxypropyl acetate and 20 parts of dimethylaminoethyl methacrylate as the second block (A block) monomer were added to this reactor, and the reaction was continued while stirring while maintaining the temperature at 110 °C in a nitrogen atmosphere. Two hours after the addition of dimethylaminoethyl methacrylate, the polymerization solution was sampled for solid content measurement, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of non-volatile content. The reaction solution was cooled to room temperature to stop the polymerization. As a result of GPC measurement, the Mw of the polymer was 9900, the molecular weight distribution Mw / Mn was 1.2, and the reaction conversion rate was 98.5%. In this way, an acrylic block copolymer (E-1) with an amine value of 71.4 mgKOH / g per solid content was obtained. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 °C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was added to the previously synthesized block copolymer solution so that the non-volatile content became 50 mass% to prepare an acrylic block copolymer (E-1) solution.

[0314] (Production Examples of Acrylic Block Copolymers (E-2 to E-8): AB-Type Block Polymers) Synthesis was carried out in the same manner as in the acrylic block copolymer (E-1) except that the raw materials and charged amounts described in Table 1 were used, and solutions of acrylic block copolymers (E-2) to (E-8) were obtained.

[0315] The compounding ratios, amine values, and weight-average molecular weights of the respective acrylic block copolymers were as shown in Table 3.

[0316]

Table 3

[0317] (Resin-type dispersant (EB-9) solution) 10 parts of methacrylic acid, 90 parts of methyl methacrylate, 50 parts of ethyl acrylate, 50 parts of tert-butyl acrylate, and 50 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel equipped with a gas introduction tube, temperature controller, condenser, and stirrer, and replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 °C, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90 °C, and a solution prepared by adding 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate was added while reacting for 7 hours. It was confirmed by solid content measurement that 95% of the reaction had occurred. 19 parts of pyromellitic dianhydride, 50 parts of propylene glycol monomethyl ether acetate, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene were added as a catalyst, and the reaction was carried out at 100 °C for 7 hours. The reaction was terminated after confirming by acid value measurement that 98% or more of the acid anhydride was half-esterified. Propylene glycol monomethyl ether acetate was added and diluted to a solid content of 50% by solid content measurement to obtain a solution of a carboxylic acid resin type dispersant (EB-9) with an acid value of 70 and a weight average molecular weight of 8,500.

[0318] [Example 1] (Preparation of Coloring Composition (RP-1)) After stirring and mixing the following mixture to make it uniform, it was dispersed using zirconia beads with a diameter of 0.5 mm for 5 hours with an Eiger mill ("Mini Model M-250MKII" manufactured by Eiger Japan Co., Ltd.), and then filtered through a 5.0 μm filter to prepare a coloring composition (RP-1). 11.4 parts of red pigment (A-1) 0.3 part of quinophthalone-based pigment derivative (B1-2) 0.3 part of quinoline-based pigment derivative (B2-2) 20.0 parts of binder resin solution (C1-1) 8.0 parts of resin type dispersant solution (E-1) 11.2 parts of organic solvent (D1-1) 48.8 parts of propylene glycol monomethyl ether acetate

[0319] [Examples 2 to 105, Comparative Examples 1 to 9] (Preparation of Coloring Compositions (RP-2 to 114)) Coloring compositions (RP-2 to 114) were prepared in the same manner as the coloring composition (RP-1), except that the composition of the red pigment (A-1), quinophthalone-based pigment derivative (B1-2), quinoline-based pigment derivative (B2-2), binder resin (C-1), resin type dispersant (E-1), and organic solvent (D-1) was changed to the composition shown in Table 4.

[0320]

Table 4-1

[0321]

Table 4-2

[0322]

Table 4-3

[0323]

Table 4-4

[0324]

Table 4-5

[0325]

Table 4-6

[0326]

Table 4-7

[0327]

Table 4-8

[0328]

Table 4-9

[0329]

Table 4-10

[0330] <Evaluation of the coloring composition> (Evaluation of initial viscosity) The viscosity of the obtained coloring composition immediately after preparation was measured and evaluated using an E-type viscometer. The evaluation criteria are as follows, and a value of 2 or more is considered practical. 5: Viscosity is 3.00 or more and less than 5.00 4: Viscosity is 5.00 or more and less than 7.00 3: Viscosity is 7.00 or more and less than 9.00 2: Viscosity is 9.00 or more and less than 11.00 1: Viscosity is 11.00 or more

[0331] (Evaluation of storage stability (viscosity evaluation)) The viscosity of the obtained coloring composition immediately after preparation and after storage at 5 °C → 23 °C → 40 °C → 5 °C for one week at each temperature was measured using an E-type viscometer. The ratio of |(viscosity after storage) - (viscosity immediately after adjustment)| / (viscosity immediately after adjustment) was calculated and evaluated according to the following criteria. The evaluation criteria are as follows, and a value of 2 or more is considered practical. 5: Viscosity ratio is less than 0.03 4: Viscosity ratio is 0.03 or more and less than 0.05 3: Viscosity ratio is 0.05 or more and less than 0.08 2: Viscosity ratio is 0.08 or more and less than 0.10 1: Viscosity ratio is 0.10 or more

[0332] (Evaluation of filterability) 10 g of the obtained coloring composition was passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number; 39115221) under a nitrogen pressure (0.3 MPa), the amount obtained through the filter was measured, and it was evaluated according to the following criteria. The evaluation criteria are as follows, and a value of 2 or more is considered practical. 5: The filtration amount is 9.0 g or more 4: The filtration amount is 7.0 g or more and less than 9.0 g 3: The filtration amount is 5.0 g or more and less than 7.0 g 2: The filtration amount is 3.0 g or more and less than 5.0 g 1: The filtration amount is less than 3.0 g

[0333] (Evaluation of storage stability (filtration property evaluation)) The filterability immediately after the preparation of the obtained coloring composition and after storing at each temperature of 5°C → 23°C → 40°C → 5°C for one week each was measured using the same measurement method. The ratio of (filterability after storage) / (filterability immediately after adjustment) was calculated and evaluated according to the following criteria. The evaluation criteria are as follows, and a value of 2 or more is considered practical. 5: The filterability ratio is 0.99 or more 4: The filterability ratio is 0.97 or more and less than 0.99 3: The filterability ratio is 0.95 or more and less than 0.97 2: The filterability ratio is 0.93 or more and less than 0.95 1: The filterability ratio is less than 0.93

[0334]

Table 5-1

[0335]

Table 5-2

[0336] The coloring composition of the present invention showed good results in both filterability and storage stability.

[0337] <Method for producing a photosensitive coloring composition>

[0338] (Preparation of Coloring Composition (RP-115)) The following mixture was stirred and mixed uniformly, and then dispersed with zirconia beads with a diameter of 0.5 mm using an Eiger mill ("Mini Model M-250MKII" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then filtered through a 5.0 μm filter to prepare a coloring composition (RP-115). Red pigment (A-1) 11.4 parts Quinophthalone-based dye derivative (B1-2) 0.3 part Quinoline-based dye derivative (B2-2) 0.3 part Binder resin solution (C1-1) 20.0 parts Resin-type dispersant solution (E-1) 8.0 parts Propylene glycol monomethyl ether acetate 60.0 parts

[0339] (Preparation of Coloring Composition (RP-116)) The following mixture was stirred and mixed uniformly, and then dispersed with zirconia beads with a diameter of 0.5 mm using an Eiger mill ("Mini Model M-250MKII" manufactured by Eiger Japan Co., Ltd.) for 5 hours, and then filtered through a 5.0 μm filter to prepare a coloring composition (RP-116). Red pigment (A-2) 11.4 parts Dye derivative (B-6) 0.6 part Binder resin solution (C1-1) 20.0 parts Resin-type dispersant solution (E-1) 8.0 parts Propylene glycol monomethyl ether acetate 60.0 parts

[0340] [Example 201] (Manufacture of Photosensitive Coloring Composition (RR-1)) The mixture having the following composition was stirred and mixed uniformly, and then filtered through a filter with a pore diameter of 1.0 μm to obtain a red photosensitive coloring composition (RR-1). Coloring composition (RP-1) 16.28 parts Coloring composition (RP-115) 33.72 parts Binder resin solution (C2-1) 3.60 parts Epoxy compound ("EHPE-3150" manufactured by Daicel) 0.16 part Photopolymerizable compound ("Aronix M402" manufactured by Toagosei Co., Ltd.) 1.16 parts Photopolymerizable compound ("Aronix M350" manufactured by Toagosei Co., Ltd.) 1.45 parts Photoinitiator ("NCI-831" manufactured by ADEKA) 0.05 part Photoinitiator ("OXE-04" manufactured by BASF) 0.05 part Photoinitiator ("SPI-02" manufactured by Samyang) 0.05 part Photoinitiator (photoinitiator represented by the following formula (31)) 0.30 part Sensitizer ("KAYACURE DETX-S" manufactured by Nippon Kayaku Co., Ltd.) 0.05 part Thiol compound (pentaerythritol tetrakis(thiopropionate)) 0.20 part Leveling agent ("BYK-330" manufactured by BYK-Chemie) 0.025 part Leveling agent (1% PGMAc solution of DOWSIL FZ-2122 (manufactured by Dow Corning Toray Co., Ltd.) 0.025 part UV absorber ("Tinuvin 326" manufactured by BASF) 0.04 part Propylene glycol monomethyl ether acetate 22.84 parts Ethyl 3-ethoxypropionate 10.00 parts Propylene glycol monomethyl ether 10.00 parts

[0341] Formula (31) [Chemical formula]

[0342] [Examples 202 to 305, Comparative Examples 101 to 109] (Production of photosensitive coloring compositions (RR-2 to 114) The photosensitive coloring compositions (RR-2 to 114) were prepared in the same manner as in Example 201, except that the coloring composition (RP-1) and the coloring composition (RP-116) were changed to the coloring composition species described in Table 6, and the ratios of the two coloring compositions were adjusted to have the same chromaticity as in Example 201.

[0343]

Table 6-1

[0344]

Table 6-2

[0345] <Evaluation of Photosensitive Coloring Composition> The obtained photosensitive coloring compositions were evaluated by the following method. The results are shown in Table 7.

[0346] (Evaluation of Initial Viscosity) The viscosity of the obtained photosensitive coloring composition immediately after preparation was measured and evaluated using an E-type viscometer. The evaluation criteria are as follows, and a value of 2 or more is considered practical. 5: Viscosity is 3.00 or more and less than 5.00 4: Viscosity is 5.00 or more and less than 7.00 3: Viscosity is 7.00 or more and less than 9.00 2: Viscosity is 9.00 or more and less than 11.00 1: Viscosity is 11.00 or more

[0347] (Evaluation of Storage Stability (Viscosity Evaluation)) The viscosity of the obtained photosensitive coloring composition immediately after preparation and after storage at 5°C → 23°C → 40°C → 5°C for 1 week at each temperature was measured using an E-type viscometer. The ratio of |(Viscosity after storage) - (Viscosity immediately after adjustment)| / (Viscosity immediately after adjustment) was calculated and evaluated according to the following criteria. The evaluation criteria are as follows, and a value of 2 or more is considered practical. 5: Viscosity ratio is less than 0.03 4: Viscosity ratio is 0.03 or more and less than 0.05 3: Viscosity ratio is 0.05 or more and less than 0.08 2: Viscosity ratio is 0.08 or more and less than 0.10 1: Viscosity ratio is 0.10 or more

[0348] (Evaluation of filterability) 10 g of the obtained photosensitive colored composition was passed through a filter (φ0.2 μm, manufactured by ADVANTEC, model number; 39115221) under a nitrogen pressure of 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, and a value of 2 or more is considered practical. 5: Filtration amount is 9.0 g or more 4: Filtration amount is 7.0 g or more and less than 9.0 g 3: Filtration amount is 5.0 g or more and less than 7.0 g 2: Filtration amount is 3.0 g or more and less than 5.0 g 1: Filtration amount is less than 3.0 g

[0349] (Evaluation of storage stability (filterability evaluation)) The filterability of the obtained photosensitive colored composition immediately after preparation and after storage at 5°C → 23°C → 40°C → 5°C for one week at each temperature was measured using the same measurement method. The ratio of (filterability after storage) / (filterability immediately after adjustment) was calculated and evaluated according to the following criteria. The evaluation criteria are as follows, and a value of 2 or more is considered practical. 5: Filterability ratio is 0.99 or more 4: Filterability ratio is 0.97 or more and less than 0.99 3: Filterability ratio is 0.95 or more and less than 0.97 2: Filterability ratio is 0.93 or more and less than 0.95 1: Filterability ratio is less than 0.93

[0350] (Foreign matter evaluation) The obtained photosensitive colored composition was applied onto a glass substrate using a spin coater such that the chromaticity value of the coating film after heat treatment was x = 0.60 under a C light source. Next, it was dried at 70°C for 20 minutes, exposed using a predetermined mask and an ultra-high pressure mercury lamp at an illuminance of 30 mW / cm2 and 50 mJ / cm2, spray-developed with an aqueous sodium carbonate solution at 23°C, washed with ion-exchanged water, and air-dried to form pattern pixels. Thereafter, heat treatment was performed in an oven at 230°C for 40 minutes, and the number of foreign substances on the glass substrate between the pattern pixels was measured. The evaluation was carried out by surface observation using a metallurgical microscope "BX60" (manufactured by Olympus Corporation). The magnification was set to 500 times, and the number of foreign substances observable in an arbitrary 5 fields of view by transmission was integrally measured. Three or more is considered practical. 5: The number of foreign substances is less than 5 4: The number of foreign substances is 5 or more and less than 10 3: The number of foreign substances is 10 or more and less than 20 2: The number of foreign substances is 20 or more and less than 50 1: The number of foreign substances is 50 or more

[0351] (Water stain evaluation) Regarding the obtained photosensitive colored composition, it was applied onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a vertical size of 100 mm × horizontal size of 100 mm and a thickness of 0.7 mm by the spin coating method such that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70°C for 1 minute. Next, ultraviolet exposure was performed using a high-pressure mercury lamp through a mask having a 100-μm-wide stripe pattern under the conditions of an illuminance of 30 mW / cm 2 and 50 mJ / cm 2 . Thereafter, it was immersed in a 0.2 mass% aqueous potassium hydroxide solution at 23°C for 40 seconds for development and washed with pure water. The surface of the obtained pattern was observed using an ECLIPSE LV100POL Model optical microscope manufactured by Nikon Corporation, and the degree of discolored portions was evaluated. The evaluation criteria are as follows, and three or more is considered practical. 5: There was no water stain. 4: The water stain was less than 10% of the whole. 3: The water stain was 10% or more and less than 20% of the whole. 2: The water stain was 20% or more and less than 30% of the whole. 1: The water stain was 30% or more of the whole.

[0352] (Pattern shape evaluation: cross-sectional shape) The obtained photosensitive coloring composition was applied onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm by spin coating method so that the film thickness after drying was 2.0 μm, and dried on a hot plate at 70 °C for 1 minute. Next, after cooling this substrate to room temperature, using a high-pressure mercury lamp, through a photomask of a 100-μm-wide stripe pattern, the illuminance was 30 mW / cm 2 , 50 mJ / cm 2 and exposed. Then, this substrate was spray-developed using an aqueous developer containing 0.2 mass% potassium hydroxide aqueous solution at 23 °C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230 °C for 30 minutes. The spray development was performed at the shortest time capable of forming a pattern without any remaining development for the film of each photosensitive coloring composition. The cross-sectional shape of the pattern was confirmed using a scanning electron microscope ("S-3000H" manufactured by Hitachi High-Technologies Corporation). The evaluation was performed by capturing an SEM image of the cross-section of a 100-μm-wide stripe pattern and measuring the taper angle between the substrate and the end of the pattern cross-section. The evaluation criteria are as follows, and a value of 3 or more is considered practical. 5: Taper angle of 30 degrees or more and less than 50 degrees 4: Taper angle of 50 degrees or more and less than 60 degrees 3: Taper angle of 30 degrees or more and less than 40 degrees, or 60 degrees or more and less than 70 degrees 2: Taper angle of 20 degrees or more and less than 30 degrees, or 70 degrees or more and less than 90 degrees 1: Taper angle of less than 20 degrees, or 90 degrees or more

[0353] [Light resistance evaluation] The coated substrate prepared in the same manner as the above pattern shape evaluation was spectroscopically analyzed using the C light source of a microspectrophotometer (Olympus "OSP-SP100"), and [L*(1), a*(1), b*(1)] were measured. Next, using a xenon lamp with a spectral distribution equivalent to sunlight, an accelerated exposure test was conducted at 470 W / m 2 for 200 hours. Thereafter, the chromaticity [L*(2), a*(2), b*(2)] was measured, and the color difference ΔE was determined by the following formula (1). Formula (1) ΔE = [[L*(2) - L*(1)] 2 + [a*(2) - a*(1)] 2 + [b*(2) - b*(1)] 2 1 / 2 A smaller color difference ΔE indicates less discoloration upon light irradiation and a coloring composition with good light resistance. Each sample was evaluated according to the following criteria. A value of 3 or more was considered practical. 5: ΔE before and after the test is less than 0.5 4: ΔE before and after the test is 0.5 or more and less than 1.0 3: ΔE before and after the test is 1.0 or more and less than 3.0 2: ΔE before and after the test is 3.0 or more and less than 5.0 1: ΔE before and after the test is 5.0 or more

[0354]

Table 7-1

[0355]

Table 7-2

[0356] From the results in Table 7, by using the coloring composition of the present invention, it was possible to have high storage stability and filterability while improving water bleeding and shape.

[0357] <Fabrication of Color Filter> ​A green photosensitive coloring composition and a blue photosensitive coloring composition used for manufacturing a color filter were prepared. For red, the photosensitive coloring composition (RR-1) of the present invention was used.

[0358] (Preparation of green coloring composition (GP-1)) After stirring and mixing the mixture of the following composition to make it uniform, it was dispersed for 5 hours using zirconia beads with a diameter of 0.5 mm in an Eiger mill (Mini Model M-250MKII manufactured by Eiger Japan Co., Ltd.), and then filtered through a filter with a pore size of 5.0 μm to prepare a green coloring composition (GP-100). Green pigment (C.I. Pigment Green 58) 8.6 parts Yellow pigment (C.I. Pigment Yellow 138) 3.4 parts Binder resin solution (C1-1) 20.0 parts Resin type dispersant solution (E-1) 8.0 parts Organic solvent (D1-1) 11.2 parts Propylene glycol monomethyl ether acetate 48.8 parts

[0359] (Preparation of green photosensitive coloring composition (GR-1)) After stirring and mixing the mixture of the following composition to make it uniform, it was filtered through a filter with a pore size of 1.0 μm to prepare a green photosensitive coloring composition (GR-1). Green coloring composition (GP-1) 42.0 parts Binder resin solution (C2-1) 13.2 parts Photopolymerizable monomer (Aronix M402 manufactured by Toagosei Co., Ltd.) 2.8 parts Photopolymerization initiator (Irgacure 907 manufactured by BASF) 2.0 parts Sensitizer (EAB-F manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part Propylene glycol monomethyl ether acetate 39.6 parts

[0360] (Preparation of blue coloring composition (BP-1)) After stirring and mixing the mixture with the following composition to make it uniform, it was dispersed for 5 hours using zirconia beads with a diameter of 0.5 mm in an Eiger mill (Mini Model M-250MKII manufactured by Eiger Japan Co., Ltd.), and then filtered through a filter with a pore size of 5.0 μm to produce a blue coloring composition (BP-1). Blue pigment (C.I. Pigment Blue 15:6) 7.2 parts Violet pigment (C.I. Pigment Violet 23) 4.8 parts Binder resin solution (C1-1) 20.0 parts Resin type dispersant solution (E-1) 8.0 parts Organic solvent (D1-1) 11.2 parts Propylene glycol monomethyl ether acetate 48.8 parts

[0361] (Preparation of blue photosensitive coloring composition (BR-1)) After stirring and mixing the mixture with the following composition to make it uniform, it was filtered through a filter with a pore size of 1.0 μm to produce a blue photosensitive coloring composition (BR-1). Blue coloring composition (BP-1) 34.0 parts Binder resin solution (C2-1) 15.2 parts Photopolymerizable monomer (Aronix M402 manufactured by Toagosei Co., Ltd.) 3.3 parts Photopolymerization initiator (Irgacure 907 manufactured by BASF) 2.0 parts Sensitizer (EAB-F manufactured by Hodogaya Chemical Co., Ltd.) 0.4 part Propylene glycol monomethyl ether acetate 45.1 parts

[0362] A black matrix was pattern-processed on a glass substrate, and the photosensitive coloring composition (RR-1) of the present invention was applied on the substrate with a spin coater to form a colored film. The film was irradiated with an ultra-high pressure mercury lamp through a photomask at 200 mJ / cm 2It was irradiated with ultraviolet rays. Then, it was spray-developed with an alkaline developer composed of a 0.2 mass% potassium hydroxide aqueous solution to remove the unexposed portions, washed with ion-exchanged water, and the substrate was heated at 230 °C for 30 minutes to form a red filter segment. Here, the red filter segment was adjusted to have a chromaticity of x = 0.660 under a C light source after the heat treatment at 230 °C. Also, by the same method, the green filter segment was adjusted to have a chromaticity of y = 0.570 using the green photosensitive coloring composition (GR-1), and the blue filter segment was adjusted to have a chromaticity of y = 0.045 using the blue photosensitive coloring composition (BR-1), and each filter segment was formed to obtain a color filter.

[0363] By using the photosensitive coloring composition (RR-1) of the present invention for the formation of the red filter segment, it was possible to suppress crystal foreign matters in the color filter, and it could be suitably used without problems in other physical properties.

Explanation of Signs

[0364] 10 Liquid crystal display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing plate 30 Backlight unit 31 White LED light source LC Liquid crystal

Claims

1. A colored composition for a color filter, comprising a red pigment (A), a pigment derivative (B), a binder resin (C), and an organic solvent (D), wherein the pigment derivative (B) contains either a quinophthalone-based pigment derivative (B1) represented by the following general formula (1) and a quinoline-based pigment derivative (B2) represented by the following general formula (2) or a quinoline-based pigment derivative (B3) represented by the following general formula (3), and the organic solvent (D) contains an organic solvent (D1) having a hydroxyl group with a boiling point of 100°C to 200°C. A colored composition for a color filter characterized by this. General formula (1) 【Chemical 1】 [In general formula (1), R １ ~R １３ each independently represents 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, an alkoxyl group which may have a substituent, -SO ３ H, -COOH, -SO ３ H or a metal salt of -COOH, or an alkylammonium salt of -SO ３ H or -COOH. However, at least one of R １ ~R １３ is -SO ３ H, -COOH, -SO ３ H or a metal salt of -COOH, or an alkylammonium salt of -SO ３ H or -COOH.] General formula (2) [Chemical 2] In general formula (2), R ２１ to R ３３ each independently represents 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, an alkoxyl group which may have a substituent, -SO ３ H, -COOH, a metal salt of -SO ３ H or -COOH, or an alkylammonium salt of -SO ３ H or -COOH. However, at least one of R ２１ to R ３３ is -SO ３ H, -COOH, a metal salt of -SO ３ H or -COOH, or an alkylammonium salt of -SO ３ H or -COOH.] General formula (3) 【Chemical 3】 [In general formula (3), R ４１ to R ５３ each independently represents 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, an alkoxyl group which may have a substituent, -SO ３ H, -COOH, a metal salt of -SO ３ H or -COOH, or an alkylammonium salt of -SO ３ H or -COOH. However, at least one of R ４１ to R ５３ is -SO ３ H, -COOH, a metal salt of -SO ３ H or -COOH, or an alkylammonium salt of -SO ３ H or -COOH.]

2. The colored composition for a color filter according to Claim 1, characterized in that the quinophthalone-based pigment derivative (B1), the quinoline-based pigment derivative (B2), and the quinoline-based pigment derivative (B3) satisfy the mass ratio of the following formula [1]. [1] 10% ≤ mass of (B1) / (mass of (B1) + mass of (B2) + mass of (B3)) ≤ 90%

3. The colored composition for a color filter according to Claim 1, characterized in that the content of the organic solvent (D1) is 1 to 30% by mass in the organic solvent (D).

4. The colored composition for a color filter according to Claim 1, further comprising a resin-type dispersant (E) having a basic group.

5. The colored composition for a color filter according to Claim 4, characterized in that the resin-type dispersant (E) having a basic group contains an acrylic block copolymer containing at least one selected from the group consisting of structural units represented by the following general formula (4), general formula (5), and general formula (6). General formula (4) 【Chemical Formula 4】 (In general formula (4), R １０１ ~R １０３ each independently represents a hydrogen atom or a linear or cyclic hydrocarbon group which may have a substituent, and two or more of R １０１ ~R １０３ may be bonded to each other to form a cyclic structure. R １０４ represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y － represents a counter anion.) General formula (5) [Chemical Formula 5] (In general formula (5), R １０５ and R １０６ each independently represent a hydrogen atom or a linear or cyclic hydrocarbon group which may have a substituent, and R １０５ and R １０６ may be bonded to each other to form a cyclic structure. R １０４ represents a hydrogen atom or a methyl group, and X represents a divalent linking group.) General formula (6) [Chemical Formula 6] (In general formula (6), R １０７ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxyradical group, or OR １１２ . R １１２ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group. R １０８ , R １０９ , R １１０ , R １１１ each independently represents a methyl group, an ethyl group, or a phenyl group. R １０４ represents a hydrogen atom or a methyl group, and X represents a divalent linking group.)

6. The colored composition for a color filter according to Claim 1, characterized in that the binder resin (C) includes a binder resin (C1) containing an alicyclic hydrocarbon-containing monomer unit (c1) and a polymerizable unsaturated group-containing monomer unit (c2).

7. The colored composition for a color filter according to Claim 1, characterized in that the red pigment (A) is any one or more selected from the group consisting of diketopyrrolopyrrole-based pigments, azo-based pigments, and anthraquinone-based pigments.

8. The colored composition for a color filter according to any one of Claims 1 to 7, further comprising a photopolymerizable monomer and / or a photoinitiator.

9. A color filter comprising a filter segment formed from the colorant composition for a color filter according to claim 8.

10. A liquid crystal display device, comprising the color filter according to claim 9.

11. A solid-state imaging device, comprising the color filter according to claim 9.

Images