Coloring composition for color filters and color filters

Abstract

To provide a color filter coloring composition which offers improved developability, in particular, capability to suppress development residues in unexposed portions.SOLUTION: A color filter coloring composition is provided, comprising a colorant (A), photopolymerizable monomer (B), alkali-soluble photosensitive resin (C), photopolymerization initiator (D), and organic solvent, where the colorant (A) contains a green pigment, and the alkali-soluble photosensitive resin (C) contains a total of 37-75 mass% of a polycyclic alicyclic monomer unit and an aromatic ring-containing monomer unit with respect to all monomer units.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a coloring composition for color filters used in the production of color filters for use in liquid crystal displays, solid-state imaging devices, and the like. [Background technology]

[0002] In order to improve the image quality of a liquid crystal display device, the resolution of the color filter is increased, that is, the number of pixels is increased. However, as the number of pixels increases, the number of light-shielding parts such as the black matrix (BM) surrounding the pixels and the thin film transistors (TFT) for driving the liquid crystal also increases, and the ratio of light-transmitting parts per unit area of ​​the color filter, that is, the aperture ratio, decreases. As a result, the brightness of the color filter decreases and the screen display part becomes dark. To compensate for this, the illuminance of the backlight must be increased, which leads to an increase in power consumption. In other words, in order to achieve high image quality and low power consumption of a liquid crystal display device, it is necessary to take the contradictory actions of increasing the resolution of the color filter and increasing the aperture ratio, and various methods and structures such as the COA method (see Patent Document 1) have been considered.

[0003] In recent years, with the trend toward higher resolution color filters, photosensitive coloring materials for color filters are required to have more stringent conditions for the development process, and improving the developability of the unexposed areas of the pattern is recognized as an essential issue. For example, in the COA method mentioned above, the mechanism requires a design that is thicker than the pixels of conventional color filters from the viewpoint of insulation, which inevitably results in a problem of a large amount of unexposed areas remaining after development.

[0004] In order to solve the above-mentioned problem of residual unexposed areas, a common solution is to increase the developability of the resin, that is, to improve the hydrophilicity of the resin by introducing an acid group or a hydroxyl group. However, there have been other methods that reduce the residual unexposed areas by reducing crosslinking during exposure using a polymerization inhibitor as shown in Patent Document 2, and by incorporating an acid generator or an acid group to improve developability and reduce the residual unexposed areas as shown in Patent Document 3. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2004-94263 A [Patent Document 2] JP 2018-072616 A [Patent Document 3] JP 2016-130849 A Summary of the Invention [Problem to be solved by the invention]

[0006] An object of the present invention is to provide a coloring composition for color filters that has good developability, particularly that can suppress development residues in unexposed areas. [Means for solving the problem]

[0007] The coloring composition for color filters of the present invention comprises a colorant (A), a photopolymerizable monomer (B), an alkali-soluble photosensitive resin (C), a photopolymerization initiator (D), and an organic solvent, The colorant (A) includes a green pigment, The alkali-soluble photosensitive resin (C) contains polycyclic alicyclic monomer units and aromatic ring-containing monomer units in a total amount of 37 to 75 mass % of all monomer units. Effect of the Invention

[0008] According to the present invention, a color filter capable of suppressing developability, particularly development residues in unexposed areas, can be obtained. It is possible to provide a coloring composition and a color filter for use in a liquid crystal display. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0009] The terms used herein are defined as follows: "(meth)acrylate", "(meth)acrylic acid", or "(meth)acrylamide" are "acrylate and / or methacrylate", "acrylic acid and / or methacrylic acid", or "acrylamide and / or methacrylamide", respectively, unless otherwise specified. "CI" is the Color Index.

[0010] The coloring composition for color filters of the present invention (hereinafter referred to as the coloring composition) contains a colorant (A), a photopolymerizable monomer (B), an alkali-soluble photosensitive resin (C), a photopolymerization initiator (D), and an organic solvent, The colorant (A) includes a green pigment, The alkali-soluble photosensitive resin (C) contains polycyclic alicyclic monomer units and aromatic ring-containing monomer units in a total amount of 37 to 75 mass % of all monomer units.

[0011] <Colorant (A)> The colorant (A) of the present invention contains a green pigment. Examples of the green pigment include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 62, and 63. Among these, CI Pigment Green 7, 36, 58, 62, and 63 are preferred because they provide high coloring strength.

[0012] The green pigment may be an organic or inorganic pigment. Organic pigments are usually used because they have high color development and high heat resistance. Hereinafter, organic pigments, including those used in the filter segments of each color, will be exemplified by color index numbers.

[0013] Red pigments include, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 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, No. 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, pigments described in JP-A-2014-134712, and pigments described in Japanese Patent No. 6368844. Among these, from the viewpoints of heat resistance, light fastness, and transmittance of the filter segment, preferred are CI Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6,368,844, and more preferred are CI Pigment Red 177, 254, 291, 295, 296, the pigments described in JP-A-2014-134712, and the pigments described in Japanese Patent No. 6,368,844.

[0014] The red pigment may be used in combination with an orange pigment such as CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73, and / or a yellow pigment described below.

[0015] Examples of blue pigments include CI 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, and 79. Among these, CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred, and CI Pigment Blue 15:6 is more preferred, in terms of heat resistance, light resistance, and transmittance of the filter segment. The blue pigment can also be used in combination with a purple pigment.

[0016] Yellow pigments include, for example, CI 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, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, and the pigments described in JP-A-2012-226110. Preferred are CI Pigment Yellow 138, 139, 150, 185, 231, and 233, and the pigments described in JP-A-2012-226110.

[0017] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50. Among these, from the viewpoints of heat resistance, light fastness, and transmittance of the filter segment, preferred are CI Pigment Violet 19 or 23, and more preferred is CI Pigment Violet 23.

[0018] The cyan pigment is preferably a blue pigment such as CI Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, 16, or 81.

[0019] Examples of magenta pigments include purple pigments and red pigments such as CI Pigment Violet 1 and 19, and CI Pigment Red 144, 146, 177, 169 and 81. A yellow pigment can be used in combination with the magenta composition.

[0020] Inorganic pigments include, for example, titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine, iron blue, chromium oxide green, and cobalt green. , umber, synthetic iron black, etc. Inorganic pigments are used in combination with organic pigments in order to ensure good coatability, sensitivity, developability, etc. while maintaining a good balance between saturation and brightness.

[0021] The coloring composition for color filters of the present invention can contain a dye for color matching within a range that does not decrease heat resistance.

[0022] The preferred concentration of the pigment component in the non-volatile content of the coloring composition of the present invention is 100% by weight. From the viewpoint of obtaining reproducibility, the concentration is 10% by mass or more, more preferably 15% by mass or more, and most preferably 20% by mass or more. In addition, from the viewpoint of improving the stability of the coloring composition, the concentration of the pigment component is preferably 90% by mass or less, more preferably 80% by mass or less, and most preferably 70% by mass or less.

[0023] <<Micronization of pigments>> In the present invention, the pigment can be made fine by salt milling. The primary particle diameter of the pigment is preferably 20 nm or more because it disperses well in the alkali-soluble photosensitive resin. In addition, it is preferably 100 nm or less because it can form a filter segment with a high contrast ratio. A particularly preferred range is 25 to 85 nm. The primary particle diameter of the pigment was measured by a method of directly measuring the size of the primary particles from an electron micrograph of the pigment taken with a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of each primary particle of the pigment were measured, and the average was taken as the particle diameter of the pigment particle. Next, the volume of each particle of 100 or more pigment particles was calculated by approximating it to a cube of the calculated particle diameter, and the volume average particle diameter was taken as the average primary particle diameter.

[0024] The salt milling process is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded while being heated using a batch or continuous kneader such as a kneader, a two-roll mill, a three-roll mill, a ball mill, an attritor, a sand mill, or a planetary mixer, and then the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed during the salt milling process by utilizing the high hardness of the inorganic salt. By optimizing the conditions for the salt milling process of the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

[0025] Examples of the water-soluble inorganic salt include sodium sulfate. Among these, inexpensive sodium chloride (table salt) is preferable. From the viewpoints of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, and most preferably 300 to 1000 parts by mass, per 100 parts by mass of the pigment.

[0026] The water-soluble organic solvent can wet the pigment and the water-soluble inorganic salt. The water-soluble organic solvent may be any solvent that dissolves (is miscible with) water and does not substantially dissolve the inorganic salt used. In this specification, the temperature rises during salt milling, and the solvent becomes prone to evaporate, so from the viewpoint of safety, a high-boiling point solvent having a boiling point of 120°C or more is preferred. 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 water-soluble organic solvent is preferably used in an amount of 5 to 1000% by mass, and more preferably 50 to 500% by mass, based on 100% by mass of the pigment.

[0027] When the pigment is subjected to salt milling, a resin can be added as necessary. Examples of the resin include natural resin, modified natural resin, synthetic resin, and synthetic resin modified with natural resin. The resin is preferably solid at room temperature (25°C) and insoluble in water. In some embodiments, the resin is preferably partially soluble in an organic solvent. The amount of the resin used is preferably in the range of 5 to 200 parts by mass relative to 100 parts by mass of the pigment.

[0028] <Photopolymerizable monomer (B)> The photopolymerizable monomer (B) includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to form a transparent resin. Examples of the photopolymerizable monomer (B) include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, 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, and 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)acrylic acid ester of methylolated melamine, epoxy (meth)acrylate, urethane acrylate, and other various acrylic acid esters and methacrylic acid esters, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

[0029] (Photopolymerizable monomer having an acid group (B)) The photopolymerizable monomer (B) may contain a photopolymerizable monomer having an acid group, such as a sulfonic acid group, a carboxyl group, or a phosphoric acid group. Examples of photopolymerizable monomers having an acid group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates; and the like. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates, such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, with dicarboxylic acids, such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and free carboxyl group-containing oligoesters 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, and benzene-1,3,5-tricarboxylic acid, with monohydroxy monoacrylates or monohydroxy monomethacrylates, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0030] (Photopolymerizable monomer having a urethane bond (B)) The photopolymerizable monomer (B) may contain a monomer having a polymerizable unsaturated group and a urethane bond. The monomer may be, for example, a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting the alcohol with a (meth)acrylate having a hydroxyl group. Examples thereof include urethane acrylate.

[0031] Examples of the (meth)acrylate 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, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0032] Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

[0033] The photopolymerizable monomer (B) can be used alone or in combination of two or more kinds.

[0034] The blending amount of the photopolymerizable monomer (B) is preferably 1 to 50 mass %, more preferably 2 to 40 mass %, based on 100 mass % of the nonvolatile content of the colored composition. When an appropriate amount is blended, the curability and developability are further improved.

[0035] <Alkali-soluble photosensitive resin (C)> The alkali-soluble photosensitive resin (C) is a resin having a photocurable polymerizable unsaturated group and an acid group, and contains a polycyclic alicyclic monomer unit and an aromatic ring-containing monomer unit in a total amount of 37 to 75 mass% of all monomer units. The coloring composition for color filters contains the above-mentioned alkali-soluble photosensitive resin (C), which improves the affinity of the dispersant and photopolymerizable monomer (B), which cause residues, to the alkali-soluble photosensitive resin (C), and the dispersant and photopolymerizable monomer (B) are easily dissolved together with the alkali-soluble photosensitive resin (C) during development, so that residues during development can be suppressed. The content of the total units is more preferably 40 to 65 mass%.

[0036] The polycyclic alicyclic monomer is a monomer that does not contain an aromatic ring, and examples thereof include dicyclopentenyl (meth)acrylate, dicyclopentanyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate.

[0037] Examples of aromatic ring-containing monomers include styrene, α-, o-, m-, p-alkyl, nitro, cyano, and amide derivatives of styrene, benzyl (meth)acrylate, rosin (meth)acrylate, naphthalene (meth)acrylate, and anthracene (meth)acrylate.

[0038] In addition, the alkali-soluble resin (C) is preferably a resin having a glass transition temperature of 95° C. or higher, more preferably 105° C. or higher. By using a resin having a relatively high glass transition temperature as described above, the strength of the entire coating can be maintained, and a good pattern shape and good residue suppression can be stably achieved. The upper limit of the glass transition temperature is preferably 175° C. or lower. The glass transition temperature is a theoretical value calculated by the following procedures (1) to (4). Step (1): Decompose the alkali-soluble photosensitive resin (C) into homopolymers of the monomers that make it up, and calculate the molar ratio. Step (2): Replace all of the sites having polymerizable unsaturated groups in each monomer with hydrogen atoms. For example, when glycidyl methacrylate (GMA) is modified with acrylic acid (AA) to introduce a crosslinking group, the acrylic acid modified site is replaced with a hydrogen atom and treated as GMA. Step (3): Convert the molar ratio of the homopolymer of each monomer into a weight ratio. Step (4): Calculate from the Tg of the homopolymer of each monomer using the Fox formula below. Fox formula: 1 / Tg=W1 / Tg1+W2 / Tg2+···+Wn / Tgn W1 to Wn indicate the weight fractions of the monomers used, and Tg1 to Tgn indicate the glass transition temperatures (unit: absolute temperature "K") of the homopolymers of the monomers. Examples of Tg (glass transition temperature) of homopolymers of main monomers used in the calculation are shown below.

[0039] The homopolymer Tg of the monomers is shown below. Dicyclopentanyl methacrylate (DCPMA): 175℃ Styrene (St): 100℃ Glycerol monomethacrylate (GLM): 55℃ Glycidyl methacrylate (GMA): 41℃ Acrylic acid (AA): 106℃ Methacrylic acid (MAA): 228℃ Methyl methacrylate (MMA): 105℃ Butyl acrylate (BA): -45℃ Butyl methacrylate (BMA): 20℃ 2-Hydroxyethyl methacrylate (HEMA): 55℃ Benzyl acrylate (BzA): 6℃ Benzyl methacrylate (BzMA): 54℃ Viscoat #315 (Osaka Organic Chemical Industry Co., Ltd.): 35℃

[0040] For monomers other than those mentioned above, use the homopolymer Tg of the monomers listed in "Polymer Data Handbook - Basic Edition - First published in 1986."

[0041] The alkali-soluble photosensitive resin (C) is preferably a resin having a transmittance of 80% or more, more preferably 95% or more in the entire wavelength region of 400 to 700 nm. In addition to using the alkali-soluble photosensitive resin (C) alone, it can be used by mixing it with a photosensitive resin other than the alkali-soluble photosensitive resin (C) and a non-photosensitive resin. In particular, when using the alkali-soluble photosensitive resin (C) in combination, it is preferable to use it in combination with other alkali-soluble photosensitive resins (R). The alkali-soluble photosensitive resin (C) is preferably a resin into which an ethylenically unsaturated double bond has been introduced by, for example, the following methods (i), (ii) and (iii). As a result, when a coating film is formed by exposure to active energy rays, the resin is three-dimensionally crosslinked, increasing the crosslink density and improving chemical resistance. The alkali-soluble photosensitive resin (C) is not limited to the above resin. In addition, the polycyclic alicyclic monomer unit and the aromatic ring-containing monomer unit are introduced into the resin when the monomers are copolymerized.

[0042] [Method (i)] Method (i) is, for example, a method in which a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is added to a side chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers, and further, a polybasic acid anhydride is reacted with the generated hydroxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[0043] Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. These may be used alone or in combination of two or more. Glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the unsaturated monobasic acid in the next step.

[0044] Examples of the unsaturated monobasic acid include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position. These may be used alone or in combination of two or more kinds.

[0045] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., which may be used alone or in combination of two or more. If necessary, for example, to increase the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups. In addition, if tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the number of ethylenically unsaturated double bonds can be further increased.

[0046] As a method similar to the method (i), for example, there is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of the side chain carboxyl groups of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with one or more other monomers, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

[0047] [Method (ii)] Method (ii) is a method in which an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group is reacted with a side chain hydroxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with an unsaturated monobasic acid having a carboxyl group or with another monomer.

[0048] The ethylenically unsaturated monomer having a hydroxyl group is 2-hydroxyethyl (meth)acrylate. acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate Examples of the hydroxyalkyl methacrylates include hydroxyalkyl methacrylates such as cyclohexanedimethanol mono(meth)acrylate, and the like, which may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above-mentioned hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of poly(γ-valerolactone), poly(ε-caprolactone, and / or poly(12-hydroxystearic acid) can also be used. From the viewpoint of suppressing foreign matter in the coating film, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred, and from the viewpoint of sensitivity, it is preferred to use one having 2 to 6 hydroxyl groups, and glycerol mono(meth)acrylate is more preferred.

[0049] Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate, but are not limited to these, and two or more types can be used in combination.

[0050] Examples of other monomers constituting the alkali-soluble photosensitive resin (C) include methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, and the like. (meth)acrylates such as butyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate; Alternatively, examples of the monomer include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; 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.

[0051] Alternatively, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 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- N-substituted maleimides such as N-(trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimide acridine. and compounds represented by the following general formula (3), specifically, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, PO-modified (meth)acrylate of nonylphenol, etc.

[0052] General formula (1) [ka]

[0053] (In general formula (1), R6 is a hydrogen atom or a methyl group, R7 is an alkylene group having 2 or 3 carbon atoms, R8 is an alkyl group having 1 to 20 carbon atoms which may have a benzene ring, and n is an integer of 1 to 15.)

[0054] Also, ethylenically unsaturated monomers containing a phosphate ester group can be used. Examples of the ter-group-containing ethylenically unsaturated monomer include monomers that can be obtained by reacting the hydroxyl group of the above-mentioned hydroxyl-group-containing ethylenically unsaturated monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0055] <Other photosensitive resins (R)> The other photosensitive resins (R) can be synthesized, for example, by the same method as that for the alkali-soluble photosensitive resin (C). The monomers that can be used as constituent units are also the same as those for the alkali-soluble photosensitive resin (C).

[0056] <Non-photosensitive resin> Examples of non-photosensitive resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. The non-photosensitive resin is preferably alkali-soluble, and examples thereof include resins having an acidic group such as a carboxyl group, a sulfonic group, etc. Specific examples of the resin include acrylic resins having an acidic group, α-olefin / maleic acid (anhydride) copolymers, styrene / styrenesulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers.

[0057] <Photopolymerization initiator (D)> The photopolymerization initiator (D) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-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- acetophenone compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t- butylperoxycarbonyl)benzophenone and other benzophenone compounds; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone and other thioxanthone compounds; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis( triazine-based compounds such as 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;1,2-Octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); ) and other oxime ester compounds; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds. Among these, oxime ester compounds are preferred.

[0058] (Oxime ester compounds) In oxime ester compounds, the NO bond of the oxime is cleaved by absorbing ultraviolet light, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, making it possible to form patterns with a small amount of exposure. When the colorant concentration of a photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may decrease, resulting in a low degree of curing of the coating, but oxime ester compounds have high quantum efficiency, which promotes curing.

[0059] Examples of the oxime ester compound include oxime ester photopolymerization initiators described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, and the like.

[0060] The photopolymerization initiator (D) can be used alone or in combination of two or more kinds.

[0061] The content of the photopolymerization initiator (D) is preferably 0.50 to 50 parts by mass, and more preferably 1 to 30 parts by mass, based on 100 parts by mass of the colorant (A). When an appropriate amount is added, the photocurability and developability are further improved.

[0062] <Epoxy compounds> The coloring composition may contain an epoxy compound. The epoxy compound is a compound having an epoxy group. The epoxy compound includes low molecular weight compounds and high molecular weight compounds such as resins. When the coloring composition contains an epoxy compound, the heat curing is promoted by post-baking, and the heat resistance of the coating is improved.

[0063] Epoxy compounds include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalic acid, etc.). Polymers of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polymers of phenols and aromatic dimethanols (benzene dimethanol, α,α,α', α'-Benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyl dimethanol, etc.), phenols and aromatic dichloromethyls (α,α'-di Polycondensates of bisphenols and various aldehydes; glycidyl ether epoxy compounds obtained by glycidylating alcohols, alicyclic epoxy compounds, glycidylamine epoxy compounds, glycidyl ether ... Among these, glycidyl ether epoxy compounds are preferred.

[0064] Commercially available epoxy compounds include, for example, Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P, Epicoat 1004, and Epicoat 1256 (all trade names; manufactured by Mitsubishi Chemical Corporation), TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals), EPPN-501H, 502 H (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60, JER 157S65, 157S70 (trade name; manufactured by Mitsubishi Chemical Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (all trade names; manufactured by Mitsubishi Chemical Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (all trade names; manufactured by Nippon Kayaku Co., Ltd.), Celloxide 2021, EHPE-3150 (all trade names; manufactured by Daicel Corporation), Denacol EX-810, EX-830, EX-851, EX-611, EX-512, EX-421, EX-313, EX-201, EX-111 (all trade names; manufactured by Nagase ChemteX Corporation), and the like.

[0065] The epoxy compounds can be used alone or in combination of two or more kinds.

[0066] The content of the epoxy compound is preferably 0.1 to 15 mass %, more preferably 0.5 to 5 mass %, based on 100 mass % of the nonvolatile content of the coloring composition for color filters. When an appropriate amount is contained, heat resistance is improved.

[0067] <Thiol compounds> The coloring composition may contain a thiol compound. The thiol compound is a compound having a thiol group (SH group), and is preferably a polyfunctional thiol compound having a plurality of thiol groups. The thiol compound, when used together with the photopolymerization initiator (D), acts as a chain transfer agent in the radical polymerization process after irradiation with light, generating thiyl radicals that are not easily inhibited by oxygen, thereby improving the sensitivity of the coloring composition. The thiol compound is preferably a polyfunctional aliphatic thiol compound in which an SH group is bonded to an aliphatic group such as a methylene or ethylene group.

[0068] Examples of the thiol compound include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane ... Examples of the mercaptopropionate include pentaerythritol tetrakis thioglycolate, pentaerythritol tetrakis thiopropionate, pentaerythritol tetrakis (3-mercaptopropionate), dipentaerythritol hexakis (3-mercaptopropionate), trimercaptopropionic acid tris (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2- (N, N-dibutylamino) -4,6-dimercapto-s-triazine, etc. Among these, pentaerythritol tetrakis thiopropionate is preferred.

[0069] The content of the polyfunctional thiol compound is preferably from 0.05 to 100 parts by mass, and more preferably from 1.0 to 50.0 parts by mass, relative to 100 parts by mass of the colorant (A).

[0070] The coloring composition may further contain additives, such as antioxidants, sensitizers, leveling agents, storage stabilizers, adhesion improvers, and polymerization inhibitors.

[0071] <Antioxidants> The antioxidant is a compound having a radical scavenging function or a peroxide decomposition function. Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, hydroxylamine compounds, benzotriazole compounds, benzophenone compounds, salicylic acid ester compounds, and triazine compounds. The antioxidant is preferably a compound that does not contain a halogen atom. Among these, from the viewpoint of achieving both the transmittance and sensitivity of the coating film, hindered phenol compounds, hindered amine compounds, phosphorus compounds, and sulfur compounds are preferred.

[0072] The antioxidants can be used alone or in combination of two or more kinds.

[0073] The content of the antioxidant is preferably from 0.1 to 5% by mass in 100% by mass of the nonvolatile content of the colored composition.

[0074] <Sensitizer> Examples of the sensitizer include polymethine dyes such as chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and 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, and tetrapyrazinoporphyrazine derivatives. Examples of the compound include conductors, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, and 4,4'-diethylaminobenzophenone.

[0075] The sensitizers can be used alone or in combination of two or more kinds.

[0076] The content of the sensitizer is preferably from 1 to 5 parts by mass, and more preferably from 1 to 4 parts by mass, based on 100 parts by mass of the photopolymerization initiator (D).

[0077] <Leveling agent> It is preferable to add a leveling agent to the coloring composition in order to improve the coating property of the composition on the transparent substrate and the drying property of the colored coating. As the leveling agent, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used.

[0078] Examples of silicone surfactants include linear polymers formed from siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or ends.

[0079] More specifically, BYK-300, 306, 310, 313, and 31 manufactured by BYK-Chemie 5N, 320, 322, 323, 330, 331, 333, 342, 345 / 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570, FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Toray Dow Corning Co., Ltd., and 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.

[0080] The fluorosurfactant may be a surfactant or a leveling agent having a fluorocarbon chain.

[0081] More specifically, examples of the resins include Surflon S-242, S-243, S-420, S-611, S-651, and 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, and DS-21 manufactured by DIC Corporation; FC-4430 and FC-4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; and Ftergent 602A manufactured by Neos Corporation.

[0082] 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, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and 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 sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamines, alkyl alkanolamides, alkyl imidazolines, and the like.

[0083] More specifically, 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, and Lathem, manufactured by Kao Corporation, are used. PD-420, PD-430, PD-430S, PD450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-5 0, MS-60, MO-60, MS-165V, Emanone 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amiit 102, 105, 105A, 302, 320, Aminone 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, and Kyoeisha Chemical Co., Ltd.'s (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, and No. 95.

[0084] Examples of the cationic surfactant include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0085] More specifically, examples of such concentrates include Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate, all of which are manufactured by Kao Corporation.

[0086] Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates.

[0087] More specifically, examples of the antibacterial agent include Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adeka Col TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

[0088] Examples of the amphoteric surfactant include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyl dimethylamino acetate betaine; and alkyl amine oxides such as lauryl dimethylamine oxide.

[0089] More specifically, examples of such antibacterial agents include Anhythol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0090] The leveling agents can be used alone or in combination of two or more kinds.

[0091] The content of the leveling agent is preferably from 0.003 to 0.5% by mass in 100% by mass of the colored composition.

[0092] <Storage stabilizer> The storage stabilizer can improve the stability of the viscosity of the coloring composition over time. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyl trimethyl 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 content of the storage stabilizer is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the coloring agent (A).

[0093] The adhesion improver improves the adhesion between the coating film formed from the coloring composition and the transparent substrate. The adhesion improver is preferably a silane coupling agent or the like. Examples of the adhesion improver include vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth)acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of the silane coupling agent include epoxy silanes such as N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltrimethoxysilane, and N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The content of the adhesion improver is preferably 0.01 to 10 parts by mass relative to 100 parts by mass of the colorant (A).

[0094] The polymerization inhibitor can suppress photosensitivity due to diffracted light from a mask when a coating film formed from the colored composition is exposed to light, so that the cross-sectional shape of the pattern is less likely to have a reverse tapered shape. Examples of the polymerization inhibitor include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, 2-n-butyl resorcinol, and 4-n-butyl resorcinol. Examples of the polymerization inhibitor include alkyl resorcinol compounds such as 2-tert-butylresorcinol and 4-tert-butylresorcinol, alkyl hydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone and 2,5-di-tert-butylhydroquinone, phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine and tribenzylphosphine, phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, phloroglucin, etc. The content of the polymerization inhibitor is preferably 0.01 to 0.4 mass% in 100 mass% of the nonvolatile content of the coloring composition.

[0095] <Organic solvent> The coloring composition contains an organic solvent, which suppresses the viscosity and enables the formation of a coating film with good surface smoothness. Examples of the organic solvent include 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-ethoxyethylpropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylho amide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, PGMAC, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone,Examples of the esters include methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters.

[0096] The content of the organic solvent is preferably 100 to 10,000 parts by mass, and more preferably 500 to 5,000 parts by mass, based on 100 parts by mass of the colorant (A).

[0097] <Method of producing colored composition> The coloring composition is prepared by dispersing a green pigment, a dispersant, a solvent, and the like to prepare a pigment dispersion. When a dispersing aid such as a dye derivative is used during the dispersion process, the pigment can be dispersed more finely. In addition, when the pigment has high solubility in the solvent, the dispersion process may not be necessary. In addition, when two or more types of pigments are used in combination, the pigment dispersion is prepared separately. Alternatively, a pigment dispersion may be prepared by mixing a plurality of pigments. Next, the pigment dispersion, the photopolymerizable monomer (B), the alkali-soluble photosensitive resin (C), and the photopolymerization initiator (D) are mixed to prepare a coloring composition. It goes without saying that the timing of mixing each material is not limited to the above example and is arbitrary. In addition, there are low molecular weight dispersants and resin-type dispersants, and the resin-type dispersant is preferable.

[0098] The dispersion treatment can be carried out using a dispersion device 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.

[0099] The colored composition prepared as described above is a so-called resist agent, and can be used as a solvent-developable type or an alkali-developable type, with the alkali-developable type being preferred.

[0100] <Removal of large particles> In the preparation of the pigment dispersion and / or the coloring composition of the present invention, it is preferable to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of, for example, centrifugation, filtration with a sintered filter or membrane filter, etc. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

[0101] <Color filters> The color filter of this specification includes a base material (also referred to as a substrate or a transparent substrate) and filter segments formed from a coloring composition for color filters. The color filter preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of colorant used. In addition, the color filter may further have a magenta filter segment, a cyan filter segment, and a yellow filter segment. In addition, a reflective substrate may be used instead of the transparent substrate. Examples of the transparent substrate include glass substrates such as soda-lime glass, low-alkali borosilicate glass, and non-alkali aluminoborosilicate glass, and resin substrates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate. In addition, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the transparent substrate for driving the liquid crystal after panelization. The reflective substrate may be, for example, a substrate using an aluminum electrode or a metal thin film as a reflective surface. The coloring composition of the present specification is preferably used for forming a green color filter segment. The color filter of the present invention can be used not only in the manufacture of liquid crystal displays, but also in the manufacture of solid-state imaging devices, organic EL displays, quantum dot displays, electronic paper, and the like.

[0102] <Manufacturing method for color filters> It is preferable to form a color filter by first forming a black matrix on a substrate and then forming filter segments. It is also possible to form a thin film transistor (TFT) on the substrate before forming the black matrix. Examples of the black matrix include a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, and a resin film with a light-shielding agent dispersed therein.

[0103] The filter segments can be formed by photolithography. In the photolithography method, for example, a coloring composition containing a colorant of a certain color tone is applied to a transparent substrate so that the dry film thickness is about 0.2 to 5 μm to form a coating. The obtained coating (hereinafter referred to as the first coating) is exposed (irradiated with light) through a mask having a predetermined pattern. Then, the coating is developed by immersing in a solvent or an alkaline developer or spraying the developer with a spray or the like, and the uncured parts are removed to obtain a desired pattern. This process can be similarly carried out using a photosensitive coloring composition containing a colorant of another color tone to produce a color filter having filter segments of each color. In addition, a second coating (oxygen barrier film) can be formed on the first coating before exposure using polyvinyl alcohol or a water-soluble acrylic resin. This prevents the first coating from coming into contact with oxygen, thereby further improving the exposure sensitivity. In addition, the color filter can be heated to cure the uncured photopolymerizable compound in the filter segment.

[0104] Examples of the coating device include a spray coater, a spin coater, a slit coater, and a roll coater. A drying step can be carried out during coating. Examples of the drying device include a hot air oven and an infrared heater.

[0105] The developer is an alkaline developer, for example, sodium carbonate, sodium hydroxide, etc. and organic alkalis such as dimethylbenzylamine, triethanolamine, etc. The developer may further contain a defoaming agent or a surfactant.

[0106] After forming the filter segments, the color filter is laminated to the opposing substrate using a sealant, liquid crystal is injected through an injection port provided in the seal portion, the injection port is sealed, and a polarizing film or a retardation film is laminated to the outside of the substrate as required, thereby fabricating a liquid crystal display device. In addition, an overcoat film or a transparent conductive film can be formed on the color filter as required.

[0107] Examples of liquid crystal display devices include twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically concentric bend (OCB). EXAMPLES

[0108] The present invention will be described below with reference to examples, but the present invention is not limited thereto. In the examples, "parts" and "%" mean "parts by mass" and "% by mass".

[0109] First, the methods for measuring the weight average molecular weight (Mw) of a resin and the acid value of a resin will be described.

[0110] <Weight average molecular weight of resin (Mw)> The weight average molecular weight (Mw) of the resin was measured in terms of polystyrene using an HLC-8220GPC (manufactured by Tosoh Corporation) as an apparatus, two TSK-GEL SUPER HZM-N columns connected in series, and THF as a solvent.

[0111] <Acid value of resin (mgKOH / g)> The acid value of the resin is the acid value (mgKOH / g) measured according to the potentiometric titration method of JIS K0070 and converted into the non-volatile content.

[0112] <Amine value of basic resin type dispersant> The amine value of the basic resin-type dispersant is the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 and converted into non-volatile content.

[0113] The methods for producing the alkali-soluble photosensitive resin (C) (R), the fine pigment (F), the resin-type dispersion (G), and the colored composition will be described.

[0114] <Production of Alkali-Soluble Photosensitive Resin (C)(R)> (Alkali-soluble photosensitive resin solution (C1)) A reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer, such as a separable 4-neck flask, was charged with 100 parts of propylene glycol monomethyl ether acetate (PGMAC), and heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 20.3 parts of styrene, 42.9 parts of dicyclopentanyl methacrylate (DCPMA), 36.9 parts of glycidyl methacrylate, and 1.0 part of azobisisobutyronitrile as a polymerization initiator was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 18.7 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol as a catalyst, and 0.3 parts of hydroquinone were added, and the reaction was carried out for 5 hours at 120°C. The acrylic acid added forms an ester bond with the epoxy group terminal of the glycidyl methacrylate structural unit, so no carboxyl group is generated in the resin structure. Further, 31.6 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine as a catalyst were added and reacted at 120° C. for 4 hours. The added tetrahydrophthalic anhydride was carboxylic anhydride. One of the two carboxyl groups generated by cleavage of the acid site forms an ester bond with a hydroxyl group in the resin structure, and the other forms a carboxyl group terminal. PGMAC was added so that the non-volatile content became 20% by mass to obtain an acrylic resin solution. The weight average molecular weight (Mw) was 9,200.

[0115] (Alkali-soluble photosensitive resin solution (C2)) 100 parts of PGMAC was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable 4-neck flask, and heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 0.6 part of styrene, 69.2 parts of dicyclopentanyl methacrylate, 30.3 parts of glycidyl methacrylate, and 1.0 part of azobisisobutyronitrile as a polymerization initiator was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 15.4 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol as a catalyst, and 0.3 parts of hydroquinone were added, and the reaction was carried out for 5 hours at 120°C. The acrylic acid added forms an ester bond with the epoxy group terminal of the glycidyl methacrylate structural unit, so no carboxyl group is generated in the resin structure. Further, 25.9 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine as a catalyst were added and reacted for 4 hours at 120° C. The carboxylic anhydride moiety of the added tetrahydrophthalic anhydride is cleaved to generate two carboxyl groups, one of which forms an ester bond with a hydroxyl group in the resin structure, and the other forms a carboxyl group terminal. PGMAC was added so that the non-volatile content became 20% by mass to obtain an acrylic resin solution. The weight average molecular weight (Mw) was 9,000.

[0116] (Alkali-soluble photosensitive resin solution (C3)) 100 parts of PGMAC was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable 4-neck flask, and heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 9.1 parts of styrene, 57.8 parts of dicyclopentanyl methacrylate, 33.1 parts of glycidyl methacrylate, and 1.0 part of azobisisobutyronitrile as a polymerization initiator was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 16.8 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol as a catalyst, and 0.3 parts of hydroquinone were added, and the reaction was carried out for 5 hours at 120°C. The acrylic acid added forms an ester bond with the epoxy group terminal of the glycidyl methacrylate structural unit, so no carboxyl group is generated in the resin structure. Further, 28.3 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine as a catalyst were added and reacted for 4 hours at 120° C. The carboxylic anhydride moiety of the added tetrahydrophthalic anhydride is cleaved to generate two carboxyl groups, one of which forms an ester bond with a hydroxyl group in the resin structure, and the other forms a carboxyl group terminal. PGMAC was added so that the non-volatile content became 20% by mass to obtain an acrylic resin solution. The weight average molecular weight (Mw) was 9,300.

[0117] (Alkali-soluble photosensitive resin solution (C4)) 100 parts of PGMAC was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable 4-neck flask, and heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 0.6 part of styrene, 59.9 parts of dicyclopentanyl methacrylate, 39.5 parts of glycidyl methacrylate, and 1.0 part of azobisisobutyronitrile as a polymerization initiator was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 20.0 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol as a catalyst, and 0.3 parts of hydroquinone were added, and the reaction was carried out for 5 hours at 120°C. The acrylic acid added forms an ester bond with the epoxy group terminal of the glycidyl methacrylate structural unit, so no carboxyl group is generated in the resin structure. In addition, 33.7 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine as a catalyst was added and reacted for 4 hours at 120° C. The carboxylic anhydride moiety of the added tetrahydrophthalic anhydride was cleaved to generate two carboxyl groups, one of which forms an ester bond with a hydroxyl group in the resin structure, and the other forms a carboxyl group terminal. PGMAC was added so that the non-volatile content became 20% by mass to obtain an acrylic resin solution. The weight average molecular weight (Mw) was 8,900.

[0118] (Alkali-soluble photosensitive resin solution (C5)) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirrer. 207 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C and substituted with nitrogen. After that, a mixture of 23.9 parts of styrene, 50.5 parts of dicyclopentanyl methacrylate, 25.7 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours from the dropping tube. After the dripping was completed, the reaction was continued for another 3 hours to obtain a resin solution. Next, the nitrogen gas was stopped and dry air was injected for 1 hour while stirring the entire amount of the obtained resin solution, and then the solution was cooled to room temperature, and a mixture of 34.1 parts of glycidyl methacrylate, 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was dripped at 70 ° C. for 3 hours. After the dripping was completed, the reaction was continued for another 1 hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAC was added so that the non-volatile content was 20 mass% to obtain an acrylic resin solution. The weight average molecular weight (Mw) was 9,500.

[0119] (Alkali-soluble photosensitive resin solution (C6)) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. Into the reaction vessel was charged 207 parts of cyclohexanone, the temperature was raised to 80°C and the atmosphere in the reaction vessel was replaced with nitrogen. Then, a mixture of 22.9 parts of methacrylic acid, 24.8 parts of styrene, 52.4 parts of dicyclopentanyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise from the dropping tube over a period of 2 hours. After the dripping was completed, the reaction was continued for another 3 hours to obtain a resin solution. Next, the nitrogen gas was stopped and dry air was injected for 1 hour while stirring the entire amount of the obtained resin solution, and then the solution was cooled to room temperature, and a mixture of 36.0 parts of glycidyl methacrylate, 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was dripped at 70 ° C. for 3 hours. After the dripping was completed, the reaction was continued for another 1 hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAC was added so that the non-volatile content was 20 mass % to obtain an acrylic resin solution. The weight average molecular weight (Mw) was 9,100.

[0120] (Alkali-soluble photosensitive resin solution (C7)) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube, and a stirrer. A reaction vessel was charged with 207 parts of cyclohexanone, heated to 80°C, and the atmosphere in the reaction vessel was replaced with nitrogen. Then, a mixture of 39.7 parts of glycerol monomethacrylate, 19.4 parts of styrene, 40.9 parts of dicyclopentanyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile was poured into the reaction vessel through the dropping tube. After the dripping was completed, the reaction was continued for another 3 hours to obtain a resin solution. Next, the nitrogen gas was stopped and dry air was injected for 1 hour while stirring the entire amount of the obtained resin solution, and then the solution was cooled to room temperature, and a mixture of 61.6 parts of 2-methacryloyloxyethyl isocyanate (Karens MOI manufactured by Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was dripped at 70°C for 3 hours. After the dripping was completed, the reaction was continued for another 1 hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content, and PGMAC was added so that the non-volatile content was 20 mass% to obtain an acrylic resin solution. The weight average molecular weight (Mw) was 9,200, and there were.

[0121] (Alkaline-soluble photosensitive resin solution (R1)) 100 parts of PGMAC was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable 4-neck flask, and heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 6.4 parts of styrene, 40.8 parts of dicyclopentanyl methacrylate, 52.7 parts of glycidyl methacrylate, and 1.0 part of azobisisobutyronitrile as a polymerization initiator was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 26.7 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol as a catalyst, and 0.3 parts of hydroquinone were added, and the reaction was carried out for 5 hours at 120°C. The acrylic acid added forms an ester bond with the epoxy group terminal of the glycidyl methacrylate structural unit, so no carboxyl group is generated in the resin structure. Further, 36.7 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine as a catalyst were added and reacted for 4 hours at 120° C. The carboxylic anhydride moiety of the added tetrahydrophthalic anhydride is cleaved to generate two carboxyl groups, one of which forms an ester bond with a hydroxyl group in the resin structure, and the other forms a carboxyl group terminal. PGMAC was added so that the non-volatile content became 20% by mass to obtain an acrylic resin solution. The weight average molecular weight (Mw) was 9,400.

[0122] (Alkaline-soluble photosensitive resin solution (R2)) 100 parts of PGMAC was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable 4-neck flask, and heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 6.4 parts of styrene, 50.2 parts of dicyclopentanyl methacrylate, 43.5 parts of glycidyl methacrylate, and 1.0 part of azobisisobutyronitrile as a polymerization initiator was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 22.1 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol as a catalyst, and 0.3 parts of hydroquinone were added, and the reaction was carried out for 5 hours at 120°C. The acrylic acid added forms an ester bond with the epoxy group terminal of the glycidyl methacrylate structural unit, so no carboxyl group is generated in the resin structure. Further, 36.2 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine as a catalyst were added and reacted for 4 hours at 120° C. The carboxylic anhydride moiety of the added tetrahydrophthalic anhydride is cleaved to generate two carboxyl groups, one of which forms an ester bond with a hydroxyl group in the resin structure, and the other forms a carboxyl group terminal. PGMAC was added so that the non-volatile content became 20% by mass to obtain an acrylic resin solution. The weight average molecular weight (Mw) was 9,300.

[0123] Table 1 shows the total (mass %) of polycyclic alicyclic monomer units and aromatic ring-containing monomer units in all monomer units of each alkali-soluble photosensitive resin, and the glass transition temperature of each resin.

[0124] [Table 1]

[0125] <Production of finely divided phthalocyanine green pigment> (Fine Phthalocyanine Pigments (F1-1) to (F1-5)) According to the examples of JP2017-111398A, the fine phthalocyanine pigments (F1-1) to (F1-5) represented by the following chemical formulas (2) to (6) were prepared, respectively.

[0126] [ka]

[0127] [ka]

[0128] [ka]

[0129] (Finely divided zinc halide phthalocyanine pigment (F2-1)) 100 parts of halogenated zinc phthalocyanine pigment CI Pigment Green 58 (DIC "FASTGEN GREEN A110"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 70° C. This kneaded product was added to 3000 parts of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a day and night to obtain 97 parts of finely divided halogenated zinc phthalocyanine pigment (F2-1).

[0130] (Fine Phthalocyanine Pigment (F2-2)) In a 300 mL flask, 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 74 parts of bromine were charged. The mixture was heated to 130°C over 40 hours, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and ground to obtain a fine phthalocyanine pigment (F2-2). The resulting finely divided phthalocyanine pigment (A2-2) was found to have an average of 13.97 halogen atoms per molecule, including an average of 11.46 bromine atoms and an average of 2.51 chlorine atoms, as determined by fluorescent X-ray analysis using a Rigaku ZSX100E. This zinc phthalocyanine pigment was found to be a halogenated phthalocyanine pigment.

[0131] (Fine Phthalocyanine Pigment (F2-3)) In a 300 mL flask, 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 59 parts of bromine were charged. The mixture was heated to 130°C over 40 hours, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (F2-3). The obtained fine phthalocyanine pigment (A2-3) was found to have an average of 12.71 halogen atoms per molecule by fluorescent X-ray analysis, of which the average number of bromine atoms was 10.22 and the average number of chlorine atoms was 2.49, making it a halogenated zinc phthalocyanine pigment.

[0132] (Fine Phthalocyanine Pigment (F2-4)) In a 300 mL flask, 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 44 parts of bromine were charged. The mixture was heated to 130°C over 40 hours, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (F2-4). The obtained fine phthalocyanine pigment (F2-4) was found to have an average of 11.98 halogen atoms per molecule by fluorescent X-ray analysis, of which the average number of bromine atoms was 9.00 and the average number of chlorine atoms was 2.98, making it a halogenated zinc phthalocyanine pigment.

[0133] (Fine Phthalocyanine Pigment (F2-5)) A 300 mL flask was charged with 109 parts of sulfuryl chloride, 131 parts of aluminum chloride, 18 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 52 parts of bromine. The mixture was heated to 130°C over 40 hours, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, 80 parts of the mixture was obtained. The mixture was taken out into 2 kg of water at ℃, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (F2-5). The obtained fine phthalocyanine pigment (F2-5) was found to be a halogenated zinc phthalocyanine pigment with an average of 12.69 halogen atoms per molecule according to X-ray fluorescence analysis, of which the average number of bromine atoms was 8.54 and the average number of chlorine atoms was 4.15.

[0134] (Fine Phthalocyanine Pigment (F2-6)) A 300 mL flask was charged with 91 parts of sulfuryl chloride, 72 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 29 parts of bromine. The temperature was raised to 130°C for 40 hours. The mixture was heated over a period of 10 minutes, taken out into water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1L twin-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (F2-6). The obtained fine phthalocyanine pigment (F2-6) was a halogenated zinc phthalocyanine pigment with an average of 8.88 halogen atoms per molecule according to fluorescent X-ray analysis, of which the average number of bromine atoms was 6.90 and the average number of chlorine atoms was 1.98.

[0135] <Production of fine yellow pigment> (Fine yellow pigments (F3-1)~(F3~3)) According to the examples of JP 2012-226110 A, finely divided quinophthalone pigments (F3-1) to (F3-3) represented by the following chemical formulas (7) to (9) were prepared. Their structures are shown below.

[0136] [ka]

[0137] (Fine Yellow Pigment (F3-4)) Quinophthalone yellow pigment CI Pigment Yellow 138 (PY138) (BASF 100 parts of "Paliotol Yellow K0960-HD" manufactured by Inoue Seisakusho Co., Ltd., 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80° C. This mixture was poured into 2000 parts of warm water, heated to 80° C. and stirred for 1 hour to form a slurry, which was then filtered and washed repeatedly to remove the salt and solvent, and then dried at 80° C. overnight to obtain 95 parts of a finely divided yellow pigment (F3-4).

[0138] (Fine Yellow Pigment (F3-5)) 100 parts of isoindoline yellow pigment CI Pigment Yellow 139 (Ciba Japan "Irgaphor Yellow 2R-CF"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader and kneaded for 10 hours at 60°C. Next, this mixture was poured into 3 liters of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to make a slurry, filtered and washed with water repeatedly to remove sodium chloride and the solvent, and then dried at 80°C for one day and night to obtain a fine yellow pigment (F3-5).

[0139] (Fine Yellow Pigment (F3-6)) Metal complex yellow pigment (CI Pigment Yellow 150, manufactured by LANXESS) 100 parts of "Yellow Pigment E4GN", 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 10 hours. Next, this mixture was poured into 3 liters of warm water, and while heating to about 80°C, it was stirred with a high-speed mixer for about 1 hour to make a slurry, which was filtered and washed repeatedly with water to remove the sodium chloride and solvent, and then dried at 80°C for one day and night to obtain a finely divided yellow pigment (F3-6). The average primary particle size was 36.6 nm.

[0140] (Fine Yellow Pigment (F3-7)) 500 parts of isoindoline yellow pigment CI Pigment Yellow 185 (BASF Japan, Paliotol Yellow D1155), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader and kneaded for 8 hours at 120° C. Next, this kneaded mixture was poured into 5 liters of warm water and stirred for 1 hour while heating to 70° C. to form a slurry. After repeatedly filtering and washing with water to remove the sodium chloride and diethylene glycol, the mixture was dried at 80° C. for one day to obtain a finely divided yellow pigment (F3-7).

[0141] [ka]

[0142] <Production of Resin-Type Dispersant (G)> (Preparation of Acidic Resin-Type Dispersant (G1-1) Solution) A reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer was charged with 3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of PGMAC, and 0.1 parts of dimethylbenzylamine. After replacing the atmosphere with nitrogen gas, the reaction vessel was heated to 120°C and reacted for 4 hours, and then at 80°C for 2 hours. Further, 30 parts of tertiary butyl acrylate, ETERNACOLL OXMA (methacrylic acid (3-ethyl oxalate), Tan-3-yl)methyl (Ube Industries, Ltd.) 20 parts, methacrylic acid 5 parts, ethyl acrylate 40 parts of dimethylformamide and 10 parts of PGMAC were charged, and 0.2 parts of 2,2'-azobisisobutyronitrile was added in 15 portions every 30 minutes while keeping the temperature inside the reaction vessel at 80°C. The non-volatile content was measured 1 hour after the final color was added, and it was confirmed that 95% of the monomer had reacted in the coat. PGMAC was added to dilute the solution so that the non-volatile content was 40%, and a resin-type dispersant (G1-1) solution with a carboxyl group and an acid value of 51 mgKOH / g per non-volatile content and a weight average molecular weight (Mw) of 24,000 was obtained.

[0143] (Preparation of Acidic Resin-Type Dispersant (G1-2 to G1-6) Solutions) Except for changing the blending amounts as shown in Table 2, the resin-type dispersant (G1-2) to (G1-6) solutions were synthesized and prepared in the same manner as the resin-type dispersant (G1-1) solution, to obtain resin-type dispersant (G1-2) to (G1-6) solutions.

[0144] [Table 2]

[0145] <Abbreviations in the table> tBA: tert-butyl acrylate OXMA: ETERNACOLL OXMA (Methacrylic acid (3-ethyloxetane-3 (-yl)methyl), manufactured by Ube Industries MAA: Methacrylic acid EA: Ethyl acrylate MMA: Methyl methacrylate AIBN: 2,2'-azobisisobutyronitrile

[0146] (Preparation of Acidic Resin-Type Dispersant (G1-7) Solution) Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 80 parts of n-butyl acrylate, 60 parts of methyl methacrylate, 20 parts of methacrylic acid, 20 parts of Karenz MOI-BM (manufactured by Showa Denko K.K.), 20 parts of ETERNACOLL OXMA (manufactured by Ube Industries, Ltd.), PG 100 parts of MAC was charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 14 parts of 2-mercapto-2-methyl-1,3-propanediol was added and reacted for 10 hours. A non-volatile content measurement confirmed that 95% of the coat had reacted. Next, 39 parts of BPAF (9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride) (manufactured by JFE Chemical Co., Ltd.), 106 parts of C-1015N (bifunctional polycarbonate polyol, trade name Kuraray Polyol C-1015N (hydroxyl value 112 mgKOH / g, manufactured by Kuraray Co., Ltd.)), 33 parts of trimellitic anhydride, 392 parts of cyclohexanone, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100 ° C. for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value. The non-volatile content was adjusted to 40% with PGMAC, and a resin-type dispersant (G1-7) solution with an acid value of 94 mgKOH / g and a weight average molecular weight of 25,000 was obtained.

[0147] (Basic resin type dispersant (G2-1) solution) In a reaction apparatus equipped with a gas inlet tube, condenser, stirring blade, and thermometer, 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was replaced 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 PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to initiate polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and the coat with a polymerization conversion rate of 98% or more was confirmed by converting it into a nonvolatile color. Next, Then, 61 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethyl benzyl dimethyl ammonium chloride were added to the reactor, and the reaction was continued by stirring while maintaining 110°C under a nitrogen atmosphere. After 2 hours of addition, the polymerization solution was sampled and the non-volatile content was measured, and the polymerization conversion rate of the second block (A block) was confirmed to be 98% or more in terms of the non-volatile content, and the reaction solution was cooled to room temperature to stop the polymerization. As a result of GPC measurement, the mass average molecular weight of the polymer was 20,000, the molecular weight distribution Mw / Mn was 1.4, and the reaction conversion rate was 98.5%. In this way, a basic resin-type dispersant (G2-1) of an AB block polymer with an amine value of 169.8 mg KOH / g per non-volatile content was obtained. After cooling to room temperature, approximately 2 g of the resin-type dispersant solution was sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content. PGMAC was added to the previously synthesized basic resin-type dispersant (G2-1) so that the non-volatile content was 30 mass %, to prepare a basic resin-type dispersant (G2-1) solution.

[0148] (Basic resin type dispersant (G2-2) solution) A reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer was charged with 133 parts of PGMAc, and the temperature was raised to 110°C while replacing with nitrogen. A dropping vessel was charged with 177 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate, 3 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of PGMAc, and 6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and after stirring until homogeneous, the mixture was dropped into the reaction vessel over 2 hours, and the reaction was continued at the same temperature for 3 hours. In this way, a basic resin type dispersant (G2-2) with an amine value of 201 mgKOH / g per nonvolatile content and a number average molecular weight of 3,800 (Mn) was obtained. The solution was diluted in the same manner as the basic resin type dispersant (G2-1) solution to prepare a basic resin type dispersant (G2-2) solution.

[0149] (Solution of salt (G3-1) of phenylphosphonic acid and basic resin-type dispersant having amino group) In a 100 mL round-bottom flask, 12.6 parts by mass of a basic resin-type dispersant (methyl methacrylate / dimethylaminoethyl methacrylate copolymer: mass ratio 5 / 3) was dissolved in 35 parts by mass of PGMAc, 2.4 parts by mass (0.5 molar equivalent relative to dimethylaminoethyl methacrylate) of phenylphosphonic acid, which is a salt-forming component, was added, and the mixture was stirred at a reaction temperature of 40°C for 2 hours to prepare a 30% by mass non-volatile solution of a salt of phenylphosphonic acid and a basic resin-type dispersant having an amino group (G3-1).

[0150] (Solution of salt (G3-2) of phenylphosphonic acid and basic resin-type dispersant having an amino group and an ammonium salt) In a 100 mL round-bottom flask, 12.6 parts by mass of a basic resin-type dispersant (methyl methacrylate / dimethylaminoethyl methacrylate / dimethylaminoethyl methacrylate methyl chloride salt copolymer: mass ratio 3 / 3 / 2) was dissolved in 35 parts by mass of PGMAc, 2.4 parts by mass of phenylphosphonic acid (0.5 molar equivalent relative to dimethylaminoethyl methacrylate), which is a salt-forming component, was added, and the mixture was stirred at a reaction temperature of 40°C for 2 hours to prepare a 30% by mass non-volatile solution of a salt of phenylphosphonic acid, an amino group, and a basic resin-type dispersant having an ammonium salt (G3-2).

[0151] <Method for producing colored composition (single color)> [Production Example 1] (Preparation of Colored Composition (A1-1)) The mixture below was stirred and mixed until homogeneous, then dispersed in an Aiga Mill ("Mini Model M-250 MKII" manufactured by Aiga Japan) using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a filter with a pore size of 5.0 μm to produce a colored composition (A1-1) with a non-volatile content of 24.3 mass%. Green pigment (F1-1): 20.5 parts Resin-type dispersant solution (G1-1: non-volatile content 30%): 1.0 part Basic resin type dispersant solution (G2-1: non-volatile content 30%): 1.0 part Alkali-soluble resin solution (R1: non-volatile content 20%): 16.0 parts Solvent (O): 61.5 parts The solvent (O) was prepared by mixing the following (O-1) to (O-6) in their respective parts by mass. (O-1)PGMAc 30 parts (O-2) Cyclohexanone 30 parts (O-3) Ethyl 3-ethoxypropionate 10 parts (O-4) Propylene glycol monomethyl ether 10 parts (O-5) Cyclohexanol acetate 10 parts (O-6) Dipropylene glycol methyl ether acetate 10 parts

[0152] [Manufacturing Examples 2-34] (Preparation of Colored Compositions (A1-2) to (A1-34)) Colored compositions (A1-2) to (A1-34) were prepared in the same manner as in Production Example 1, except that the material types and masses were changed as shown in Table 3.

[0153] [Table 3]

[0154] <Method for producing coloring composition (coloring material mixture)> [Example 101] (Preparation of Colored Composition (A2-1)) The following raw materials were mixed and stirred, and then filtered through a filter having a pore size of 1.0 μm to obtain a colored composition (X-1). Coloring composition (A1-1: non-volatile content 24.3%): 40 parts Coloring composition (A1-27: non-volatile content 24.3%): 16 parts Alkali-soluble resin solution (R1: non-volatile content 20%): 32 parts Solvent (O): 12 parts

[0155] [Examples 102-133] (Preparation of Colored Compositions (A2-2 to A2-33)) Colored compositions (A2-2 to A2-33) were prepared in the same manner as in Production Example 101, except that the material types and masses were changed as shown in Table 4.

[0156] [Table 4]

[0157] <Method for producing photosensitive coloring composition> [Example 1] (Photosensitive coloring composition (Y-1)) The following raw materials were mixed and stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y -1). The following photopolymerizable monomer (B) was prepared by mixing ARONIX M402 and ARONIX M520 manufactured by Toagosei Co., Ltd., KAYARAD DPCA-30 manufactured by Nippon Kayaku Co., Ltd., and UA-510H manufactured by Kyoeisha Chemical Co., Ltd. in a ratio of 1: This mixture was prepared by mixing at a ratio of 1:1:1. The following photopolymerization initiators (D) are Irgacure OXE-01 manufactured by BASF Japan, Irgacure OXE-02 manufactured by BASF Japan, Irgacure OXE-04 manufactured by BASF Japan, Adeka Arcles NCI-831 manufactured by ADEKA, and Omni rad 907, IGM Resins Omnirad 369E 1:1:1:1 This is a mixture prepared by mixing in a ratio of 1:1. The polymerization inhibitor below is a mixed solution in which 1 part of "3-methylcatechol", 1 part of "methylhydroquinone", and 1 part of "tert-butylhydroquinone" are dissolved in 100 parts of PGMAC. The following leveling agent was prepared by dissolving 1 part of BYK-330 manufactured by BYK, 1 part of Megafac F-551 manufactured by DIC, and 1 part of Emulgen 103 manufactured by Kao in 100 parts of PGMAC. This is a mixed solution.

[0158] Coloring composition (A1-1: non-volatile content 24.3%): 44.0 parts Alkali-soluble photosensitive resin solution (C1: non-volatile content 20%): 10.0 parts Thermosetting compound solution (EX-611, Nagase Chemtex Corporation): 0.5 parts Photopolymerizable monomer (B): 3.0 parts Photopolymerization initiator (D): 0.4 parts Thiol chain transfer agent (pentaerythritol tetrakisthiopropionate) :0.4 parts Polymerization inhibitor: 0.2 parts Leveling agent: 1.5 parts Solvent (PGMAc): 40.0 parts

[0159] [Examples 2 to 71, Comparative Examples 1 to 4] (Preparation of Photosensitive Coloring Compositions (Y-2) to (Y-75)) Except for changing the coloring composition and the type of alkali-soluble photosensitive resin solution of Example 1 as shown in Table 5, the same procedure as in Example 1 was carried out to prepare photosensitive coloring compositions (Y-2) to (Y-75). [Table 5]

[0160] <Evaluation of Photosensitive Coloring Composition> Each test was carried out according to the following method. The test results are shown in Table 6. The meanings of the evaluation ranks are as follows: ◎: Very good, ◯: Good, △: Practical, ×: Not suitable for practical use

[0161] <Evaluation of development residue on glass substrate> The photosensitive coloring composition was applied to a 10×10 cm glass substrate using a spin coater so that the film thickness after drying would be 2 μm, and then dried under reduced pressure to form a coating film. This coating film was exposed to light from a high-pressure mercury lamp at 50 mJ / cm2 using a stripe pattern mask with a line width of 50 μm, and then spray-developed for 60 seconds using a 0.05% potassium hydroxide aqueous solution kept at 25°C, and then thoroughly washed with ion-exchanged water and dried with clean air to obtain an evaluation coating film. The presence or absence of residues on the substrate from which the coating film had been removed by development was observed using a 50x optical microscope. When no residues were found on the 10×10 cm glass substrate at all, it was marked with ⊚, and when there was only one residue, it was marked with ⊚. If residue was found in 5 or more but less than 5 places, it was rated as ◯, if residue was found in 5 or more but less than 10 places, it was rated as △, and if residue was found in 10 or more places, it was rated as ×. × is a level at which the product cannot be used.

[0162] <Evaluation of development residue on black matrix coating> [Preparation of Carbon Black Dispersion] Carbon black (Mitsubishi Chemical #47, average primary particle size 23 nm, specific surface area 132 m 2 / g, oil absorption 64cm 3 / 100g) 100 parts, 4 parts of the dye derivative shown in the following chemical formula, resin 14 parts of Solution G1-1 and 6 parts of Alkali-soluble Resin Solution R1 were mixed and diluted with cyclohexanone to adjust the non-volatile content to 20%. The resulting mixture was dispersed for 2 hours using glass beads with a diameter of 0.8 mm in a paint shaker to prepare Carbon Black Dispersion A. The viscosity of the resulting Carbon Black Dispersion A was 8.70 mPa s at 25°C.

[0163] [ka]

[0164] The photosensitive coloring composition was applied onto a black matrix (hereinafter referred to as BM) coating film that had been cured on a 10 x 10 cm glass substrate, and dried under reduced pressure to form a coating film with a thickness of 1 micron. This coating film was then exposed to a high-pressure mercury lamp at 50 mJ / cm. 2 After the entire surface was exposed to light at 400°C, it was spray-developed for 60 seconds using a 0.05% aqueous potassium hydroxide solution kept at 25°C, thoroughly washed with ion-exchanged water, dried with clean air, and then the obtained substrate was post-baked at 230°C for 30 minutes to prepare an evaluation substrate. Thereafter, the photosensitive coloring composition was applied onto a 10×10 cm glass substrate and dried under reduced pressure to form a coating film having a thickness of 2 microns. This coating film was then exposed to 50 mJ / cm 2 of high-pressure mercury lamp light using a stripe pattern mask with a line width of 50 μm. 2After exposure to light at 400 K, the film was spray-developed for 60 seconds using a 0.05% aqueous potassium hydroxide solution kept at 25°C, then thoroughly washed with ion-exchanged water and dried with clean air to obtain a coating film for evaluation. This evaluation evaluates the development residue on the BM coating film when the filter segments of each color are formed consecutively. The presence or absence of residues on the substrates from which the coating film had been removed by development was observed using a 50x optical microscope. When absolutely no residues were found on the BM of the 10x10cm evaluation substrate, they were rated as ◎, when residues were found in 1 to less than 5 places, 〇, when residues were found in 5 to less than 10 places, △, and when residues were found in 10 or more places, ×. × indicates that the substrate cannot be used.

[0165] <Pattern cross-sectional shape evaluation> The photosensitive coloring composition was applied onto a 10 x 10 cm glass substrate and dried under reduced pressure to form a coating film with a thickness of 2 microns. This coating film was exposed to light from a high-pressure mercury lamp at 50 mJ / cm2 using a stripe pattern mask with a line width of 50 μm, and then spray-developed for 60 seconds using a 0.05% potassium hydroxide aqueous solution kept at 25°C. The resulting substrate was then thoroughly washed with ion-exchanged water and dried with clean air. The resulting substrate was then post-baked at 230°C for 20 minutes to prepare an evaluation substrate. A scanning electron microscope (Hitachi High-Tech's "S-3000H") (hereinafter referred to as SEM) was used to ) to confirm the cross-sectional shape of the pattern. For evaluation, an SEM image of a 50 μm-wide stripe pattern was captured, and the angle of the tapered portion of the pattern cross section was evaluated using a protractor as follows. The angle of the tapered portion was taken as the profile angle. ◎: Profile angle less than 60° 〇: Profile angle 60° or more, less than 70° △: Profile angle 70° or more, less than 80° ×: Profile angle 80° or more

[0166] [Table 6-1]

[0167] [Table 6-2]

[0168] From the results in Table 6, it was confirmed that the alkali-soluble photosensitive resin in the coloring composition contains 37 to 75 mass% of polycyclic alicyclic monomer units and aromatic ring-containing monomer units in total among all monomer units, thereby improving the effect of residues on glass and BM. In particular, it was found that the effect of improving residues is greater by containing 40 to 65 mass% of polycyclic alicyclic monomer units and aromatic ring-containing monomer units in total among all monomer units. In addition, with regard to Tg, a good profile angle can be formed by being 95°C or higher, and particularly an extremely good profile angle can be formed by being 105°C or higher.

Claims

1. A colorant (A), a photopolymerizable monomer (B), an alkali-soluble photosensitive resin (C), a polymerization initiator (D), an acidic resin-type dispersant, and an organic solvent; The colorant (A) contains a green pigment, The alkali-soluble photosensitive resin (C) contains, in all monomer units, 35.4 to 75 mass% of polycyclic alicyclic monomer units and aromatic ring-containing monomer units in total, and 11.4 to 17.2 mass% of aromatic ring-containing monomer units; The coloring composition for color filters, wherein the acidic resin-type dispersant has an acid value of 35 to 75 mgKOH / g.

2. 2. The coloring composition for color filters according to claim 1, wherein the alkali-soluble photosensitive resin (C) is a resin having a glass transition temperature of 95° C. or higher.

3. The coloring composition for color filters according to claim 1 or 2, further comprising an epoxy compound.

4. The coloring composition for color filters according to any one of claims 1 to 3, further comprising a thiol compound.

5. A color filter comprising a substrate and a filter segment formed from the coloring composition for color filters according to any one of claims 1 to 4.

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