Photosensitive coloring composition, color filter, solid-state imaging element, liquid crystal display device, and infrared sensor

Abstract

To provide a coloring composition which is excellent in fastness such as good heat resistance, suppresses occurrences of poor uniformity (hereinafter referred to as coating unevenness) and striation, and enables production of a good film.SOLUTION: A photosensitive coloring composition contains a coloring agent (A), a resin (B), a polymerizable compound (C), a photopolymerization initiator (D) and a surface active agent (E), wherein the polymerizable compound (C) contains a compound (C1) having an alkylene oxide chain, and the surface active agent (E) is composed of a copolymer (E1) of a monomer (ED1) containing one or more selected from the group consisting of a fluorinated alkyl group and a poly(perfluoroalkylene ether) chain, and a monomer (ED2) having crosslinked ring hydrocarbon.SELECTED DRAWING: Figure 1

Description

[Technical field]

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

[0002] Solid-state imaging elements such as CCD (charge-coupled device) and CMOS (complementary metal oxide semiconductor) are used in color liquid crystal devices, smartphones, tablet terminals, and various sensors. A color filter having pixels formed using a photosensitive coloring composition is used in the solid-state imaging element. In addition, when forming a color filter, when the photosensitive coloring composition is applied on a surface having steps such as unevenness, coating unevenness or striations may occur. Patent Document 1 describes that the use of a photosensitive coloring composition containing a fluorine-based surfactant can suppress the occurrence of surface unevenness and striations. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] JP 2018-54918 A Summary of the Invention [Problem to be solved by the invention]

[0004] In the solid-state imaging device application, which is one of the applications of the photosensitive coloring composition, in order to realize fine pixels, it is necessary to produce a film by applying the coloring composition at a higher rotation rate on a support having a fine partition structure. In addition to suppressing the occurrence of striations (uneven linear patterns that are formed radially toward the periphery of the wafer when the film thickness becomes uneven when applying resist on a wafer) caused by high-rotation coating on a complex support, the coloring composition is required to be applied uniformly over the entire support. In addition, the post-bake process in forming color filters must be performed at a high temperature of generally 200° C. or higher, preferably 230° C. or higher. In the reflow process in forming solid-state imaging devices, components are soldered onto a substrate at a high temperature of 255° C. or higher. As the trend toward thinner films and finer pixels increases with increasing resolution, the pigment components contained in color filters increase, making it difficult to ensure heat resistance. Photosensitive colorants with even better heat resistance are required so that the pixels formed in the above-mentioned high-temperature processes can demonstrate their characteristics without any problems.

[0005] Furthermore, when the present inventors investigated the colored composition described in Patent Document 1, they found that the color change was large when baked at high temperatures, and striations were likely to occur during high-speed coating.

[0006] The present invention aims to provide a colored composition that has excellent fastness, such as little change in chromaticity and good heat resistance, and can form a good film by suppressing the occurrence of poor uniformity (hereinafter, coating unevenness) and striations. [Means for solving the problem]

[0007] <1> A photosensitive coloring composition comprising a colorant (A), a resin (B), a polymerizable compound (C), a photopolymerization initiator (D) and a surfactant (E), the polymerizable compound (C) contains a compound (C1) having an alkylene oxide chain, A photosensitive coloring composition, characterized in that the surfactant (E) comprises a copolymer (E1) of a monomer (ED1) containing one or more selected from the group consisting of a fluorinated alkyl group and a poly(perfluoroalkylene ether) chain, and a monomer (ED2) having a bridged ring hydrocarbon. <2> The fluorosurfactant (E) is characterized in that the bridged ring hydrocarbon skeleton contains a polymerizable monomer (ED2) having an adamantyl ring, an isobornyl ring, or a dicyclopentanyl ring. <1> The photosensitive coloring composition according to claim 1. <3> The coloring composition is characterized in that the content of the colorant (A) is 30 to 70 parts by mass and the content of the polymerizable compound (C) is 0.1 to 20.0 parts by mass per 100 parts by mass of the nonvolatile content of the coloring composition. <1> or <2> The photosensitive coloring composition according to claim 1. <4> The photopolymerization initiator (D) contains a photopolymerization initiator (D1) having an oxime ester skeleton. <1> ~ <3> The photosensitive coloring composition according to any one of the above. <5> <1> ~ <4> A color filter having filter segments formed from the photosensitive coloring composition according to claim 1. <6> <5> A solid-state imaging device comprising the color filter according to claim 1. <7> <5> A liquid crystal display device comprising the color filter according to claim 1. <8> <5> An infrared sensor comprising the color filter according to claim 1. Effect of the Invention

[0008] According to the present invention, it is possible to provide a coloring composition which has excellent fastness such as good heat resistance, and can form a good film by suppressing the occurrence of coating unevenness and striations. In addition, it is possible to provide a color filter, a solid-state imaging device, a liquid crystal display device, an infrared sensor, etc. [Brief description of the drawings]

[0009] [Figure 1] FIG. 1 is a schematic cross-sectional view of an image display device. [Diagram 2] FIG. 2 is a schematic cross-sectional view of an infrared sensor. [Diagram 3] FIG. 2 is a schematic diagram illustrating the position of a step on a silicon wafer selected when evaluating coatability in the examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The terms used in this specification are defined below. When "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" is used, it means "acryloyl and / or methacryl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively, unless otherwise specified. "CI" in this specification means Color Index (CI). Colorants include pigments and dyes. A monomer is a compound that has an ethylenically unsaturated double bond and forms a resin by polymerization. A monomer is in an unreacted state, and a monomer unit is a monomer that forms part of a resin after polymerization.

[0011] The photosensitive coloring composition of the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), a photopolymerization initiator (D) and a surfactant (E). the polymerizable compound (C) contains a compound (C1) having an alkylene oxide chain, The photosensitive coloring composition is characterized in that the surfactant (E) comprises a copolymer (E1) of a monomer (ED1) containing one or more selected from the group consisting of a fluorinated alkyl group and a poly(perfluoroalkylene ether) chain, and a monomer (ED2) having a bridged ring hydrocarbon.

[0012] The photosensitive coloring composition of the present invention can suppress the occurrence of striations during spin coating by using a copolymer (E1) having a fluorinated alkyl group or a poly(perfluoroalkylene ether) chain as a surfactant. In addition, the fluorine-based compound has a bulky and rigid bridged ring hydrocarbon structure, which improves, for example, the robustness and heat resistance of pixels. By using a compound having an alkylene oxide chain as a polymerizable compound, coating unevenness can be suppressed during spin coating of the photosensitive coloring composition.

[0013] <Colorant (A)> Examples of the colorant (A) include pigments (organic pigments and inorganic pigments) and dyes. The pigment is preferably an organic pigment having high color development and high heat resistance. Specific examples of organic pigments are shown below with their color index numbers.

[0014] 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, 2 50, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, etc. Among these, from the viewpoints of heat resistance, light resistance, and transmittance of the filter segment, CI Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, and 296 are preferred, and CI Pigment Red 177, 254, 291, 295, and 296 are more preferred.

[0015] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, and 73.

[0016] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63. Among these, CI Pigment Green 36, 58, 59, 62, or 63 is preferred from the viewpoint of transmittance.

[0017] 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, 11 8, 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, etc. Among these, CI Pigment Yellow 138, 139, 150, 185, 231, 233 are preferable.

[0018] 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, from the viewpoints of heat resistance, light resistance, and transmittance of the filter segment, preferred are CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6, and more preferred is CI Pigment Blue 15:6.

[0019] 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.

[0020] Examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, and synthetic iron black.

[0021] The content of the colorant (A) is preferably 30 to 70 parts by mass in 100 parts by mass of the total nonvolatile content of the photosensitive coloring composition.

[0022] <Dye derivative (b)> In this specification, the photosensitive coloring composition can contain a dye derivative. The dye derivative can be a known dye derivative having an acidic group, a basic group, a neutral group, or the like in the organic dye residue. For example, compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and their amine salts, compounds having a basic substituent such as a sulfonamide group or a tertiary amino group at the end, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group, can be mentioned. Since the resin-type dispersant used in combination has an acidic group, a dye derivative having a basic group is preferred. Examples of the organic dye of the organic dye residue include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo, and polyazo, and the like.

[0023] These dye derivatives can be used alone or in combination of two or more kinds.

[0024] The amount of the dye derivative used is preferably from 1 to 30 parts by mass, more preferably from 3 to 25 parts by mass, and even more preferably from 5 to 20 parts by mass, relative to 100 parts by mass of the pigment.

[0025] When a dye derivative is added to a pigment and a fine particle size treatment such as acid pasting, acid slurry, dry milling, salt milling, or solvent salt milling is performed, the dye derivative is adsorbed onto the pigment surface, which allows the primary particles of the pigment to be finer than when the dye derivative is not added.

[0026] <Minification of pigments> It is preferable that the organic pigment is mixed with other raw materials after being subjected to a micronization treatment. Examples of the method of the micronization treatment include wet grinding, dry grinding, and dissolution precipitation. Among these, a salt milling treatment using a kneader method, which is a type of wet grinding, is preferable. The average primary particle size of the organic pigment after the micronization treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. A moderate particle size improves dispersibility and the contrast ratio of the coating. The average primary particle size is the average value of about 20 particles arbitrarily selected from an enlarged image of a TEM (transmission electron microscope). When the particle has a vertical axis length and a horizontal axis length, the vertical axis length is used.

[0027] 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 salt milling by utilizing the high hardness of the inorganic salt. By optimizing the conditions for salt milling the pigment, it is possible to obtain a pigment having a very fine primary particle diameter, a narrow distribution width, and a sharp particle size distribution.

[0028] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate. Among these, sodium chloride (table salt) is preferred from the viewpoint of cost. The amount of the water-soluble inorganic salt used is preferably 50 to 2000 parts by mass, and more preferably 300 to 1000 parts by mass, per 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

[0029] The water-soluble organic solvent moistens the pigment and the water-soluble inorganic salt. The water-soluble organic solvent is a compound that dissolves (is mixed) in water and does not substantially dissolve the water-soluble inorganic salt. The water-soluble organic solvent is preferably a high-boiling solvent having a boiling point of 120°C or more, in that it is less likely to volatilize due to the temperature rise during salt milling. Examples of the water-soluble organic solvent include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, relative to 100 parts by mass of the pigment.

[0030] During the salt milling treatment, a resin can be added as necessary. Examples of the resin include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in a water-soluble organic solvent. The amount of the resin used is preferably 5 to 200 parts by mass relative to 100 parts by mass of the pigment.

[0031] <dye> Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Also included are dye derivatives and lake pigments obtained by converting dyes into lakes.

[0032] In addition, the dye may be an acid dye having an acidic group such as sulfonic acid or carboxylic acid, or in the case of a direct dye, an inorganic salt of an acid dye; a salt-forming compound of an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound; or a salt-forming compound of a resin component having an amino group and an acid dye. A salt-forming compound of an acid dye and a compound having an onium salt group is also preferable because it has excellent fastness. In addition, the compound having an onium salt group is preferably a resin having a cationic group in the side chain.

[0033] Examples of the basic dye include salt-forming compounds with organic acids, perchloric acid, or metal salts thereof. Among the salt-forming compounds, salt-forming compounds of basic dyes are preferred because they have excellent resistance to various types of substances and are compatible with pigments.

[0034] The chemical structure of the dye may be, for example, an azo dye, a disazo dye, an azomethine dye (such as an indoaniline dye or an indophenol dye), a dipyrromethene dye, a quinone dye (such as a benzoquinone dye, a naphthoquinone dye, anthraquinone dye, or anthrapyridone dye), a carbonium dye (such as a diphenylmethane dye, a triphenylmethane dye, a xanthene dye, or an acridine dye), a quinoneimine dye (such as an oxazine dye), or a quinoneimine dye (such as an oxazine dye). dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, etc. Among these, from the viewpoint of color properties such as hue, color separation, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred.

[0035] <Metal Removal> If a specific metal element is present in a large amount in the coloring composition as an impurity other than the pigment constituent, it inhibits dispersion stability over time. In addition, it may cause a decrease in heat resistance or a decrease in sensitivity. In addition, a color filter made using this may have foreign matter, which may result in a decrease in brightness. The total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) contained in the photosensitive coloring composition is preferably 500 mass ppm or less.

[0036] The total amount of the specific metal elements is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less. The lower limit of the total amount of the specific metal elements is not particularly limited, but is preferably 1 mass ppm or more, more preferably 5 mass ppm or more. Within the above range, the photosensitive coloring composition can be obtained that can suppress costs, has excellent storage stability, and can form a color filter with little generation of foreign matter and little decrease in brightness.

[0037] The amount of each specific metal element contained in the photosensitive coloring composition is preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less.

[0038] In addition, since it is desired to suppress impurities that do not constitute the pigment, such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co, which constitute the pigment, they can be removed in the same manner as the specific metal elements, for example, by the following method. Furthermore, Mn, Cs, Ti, Co, Si, Pd, etc. may be mixed in from materials (for example, catalysts) used in the manufacturing process of various raw materials for the photosensitive coloring composition, so they are removed as much as possible.

[0039] Methods for removing metals that have become mixed in from the pigment (A) or from equipment during the manufacturing process include the water washing methods described in JP-A-2010-83997, JP-A-2018-36521, JP-A-7-198928, JP-A-8-333521, JP-A-2009-7432, etc., and the method of removing magnetic foreign matter using a magnet described in JP-A-2011-48736.

[0040] The content of specific metal elements can be measured by inductively coupled plasma emission spectrometry (ICP).

[0041] <Resin (B)> The resin (B) in the present invention contains a resin-type dispersant (B1) and a binder resin (B2) which will be described later.

[0042] The content of the resin (B) is preferably from 5 to 60 parts by mass, and more preferably from 10 to 50 parts by mass, based on 100 parts by mass of the colorant (A).

[0043] <Resin-type dispersant (B1)> The resin type dispersant (B1) has a colorant adsorption site that adsorbs to the colorant and a steric repulsion site that stably disperses the colorant particles. Examples of the resin type dispersant (B1) include urethane-based dispersants such as polyurethane, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates and their modified products, oil-based dispersants such as amides formed by the reaction of poly(lower alkylene imines) with polyesters having free carboxyl groups and their salts, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohols, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphates.

[0044] The resin-type dispersant (B1) can be classified into an acidic resin-type dispersant having an acidic group and a basic resin-type dispersant having basicity, and in this specification, the acidic resin-type dispersant is preferred.

[0045] The acidic resin type dispersant is, for example, a resin having a main chain containing an aromatic carboxylic acid ester moiety having an ester bond formed by esterification reaction of an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain containing a vinyl polymer moiety. The amount of the acid anhydride group relative to 1 mole of the hydroxyl group is preferably 0.9 to 1.5 moles, more preferably 1.0 to 1.3 moles. The main chain containing the aromatic carboxylate moiety preferably has a structure having a blocking moiety derived from a monoalcohol, which will be described later, whereby the acid anhydride group in the main chain is modified to an alcohol ester group and a carboxyl group. The use of the dispersion resin (B) improves the filterability of the photosensitive coloring composition and suppresses foreign matter in the coating. Furthermore, the solidified product of the photosensitive coloring composition that is generated when the composition is applied using a tie coater or the like becomes more easily redissolved in propylene glycol monomethyl ether acetate (PGMAc) (resolubility). The side chain based on the vinyl polymer portion is generated by polymerization of the monomer.

[0046] (Aromatic compounds having two or more acid anhydride groups) Examples of aromatic compounds having two or more acid anhydride groups include pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene Tetracarboxylic acid dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

[0047] (Compounds having two or more hydroxyl groups) As described above, the compound having two or more hydroxyl groups is preferably a compound having a hydroxyl group and a thiol group in the molecule, and more preferably a compound having two hydroxyl groups and one thiol group in the molecule.

[0048] Examples of compounds having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0049] (Monoalcohol) Examples of monoalcohols include monoalcohols such as methanol, ethanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, lauryl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexanol, benzyl alcohol, and methylcyclohexanol; Examples of the monoalcohols include monoalcohols having an ether group such as 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, and propylene glycol monomethyl ether; and monoalcohols having a carbonyl group such as methyl lactate, ethyl lactate, and diacetone alcohol. These may be used alone or in combination of two or more.

[0050] The monoalcohol is preferably a compound having an ether group or a carbonyl group, and more preferably 3-methoxybutanol, propylene glycol monomethyl ether, or diacetone alcohol, which generates an ether group or a carbonyl group at the end of the main chain of the dispersion resin, thereby improving the resolubility in PGMAc.

[0051] The main chain which is an aromatic carboxylate moiety may have a blocking moiety which is reacted with water, in addition to a blocking moiety derived from a monoalcohol.

[0052] When synthesizing the capping portion, the amount of monoalcohol used relative to the acid anhydride group is preferably 1 to 30 molar equivalents relative to 1 equivalent of the acid anhydride group remaining in the main chain, and more preferably 1.5 to 20 molar equivalents. When the amount is 1 molar equivalent or more, no acid anhydride group remains, resulting in good storage stability, and when the amount is 30 molar equivalents or less, ester exchange reaction due to the ester bond between the monoalcohol and the dispersant is unlikely to occur, and a decrease in molecular weight is unlikely to occur.

[0053] (Side chain that is a vinyl polymer moiety) The side chains of the acidic resin-type dispersant can be synthesized by polymerizing a monomer in the presence of a compound having two hydroxyl groups and one thiol group in the molecule. The dispersion resin having an aromatic carboxylic acid structure can form a main chain after first forming a side chain, which is a vinyl polymer moiety, or can form a side chain by polymerizing a monomer after forming a main chain through the esterification reaction.

[0054] Examples of basic resin-type dispersants include nitrogen-atom-containing graft copolymers, nitrogen-atom-containing acrylic block copolymers having functional groups in the side chains including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, and urethane-based polymer dispersants.

[0055] In addition, as disclosed in JP 2009-185277 A, it is also preferable to use a resin-type dispersant having an aromatic carboxyl group in combination with a vinyl resin having a tertiary amino group (having the function of a resin-type dispersant).

[0056] The amount of the resin-type dispersant (B1) used is preferably 3 to 200 mass %, more preferably 5 to 100 mass %, based on 100 parts by mass of the colorant (A). When an appropriate amount is used, the film-forming property of the composition is further improved.

[0057] <Binder resin (B2)> The binder resin (B2) is preferably a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm when a coating having a thickness of 2 μm is formed. The transmittance is preferably 95% or more. Binder resins can be classified according to the curing method, and include thermoplastic resins and photosensitive resins having a polymerizable unsaturated group. The photosensitive resin can contain a thermosetting group such as an epoxy group or an oxetane group. In this specification, the binder resin (B2) is preferably an alkali-soluble resin. The alkali-soluble resin is a resin having a functional group such as a hydroxyl group, a carboxyl group, or a sulfone group. The polymerizable unsaturated group is a vinyl group, a (meth)acryloyl group, a (meth)allyl group, or the like.

[0058] <Thermoplastic resin> Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

[0059] <Alkali-soluble resin> The binder resin (B) is preferably an alkali-soluble resin in terms of developability. Examples of the alkali-soluble resin include an alkali-soluble resin (B2-1) that does not have a polymerizable unsaturated group and a photosensitive alkali-soluble resin (B2-2). The alkali-soluble resin is preferably a chain-like random polymer. The chain-like resin includes a branched chain.

[0060] The weight average molecular weight (Mw) of the alkali-soluble resin is preferably from 2,000 to 40,000, more preferably from 3,000 to 30,000, and even more preferably from 4,000 to 20,000. The value of Mw / Mn (number average molecular weight) is preferably 10 or less. When the weight average molecular weight (Mw) is within an appropriate range, the adhesion of the coating to the substrate and the developability can be highly compatible.

[0061] The acid value of the alkali-soluble resin is preferably 50 to 200 mgKOHmg / g, more preferably 70 to 180 mgKOHmg / g, and even more preferably 90 to 170 mgKOHmg / g, in terms of solubility in alkali development. A moderate acid value allows the coating film to have a high degree of adhesion to the substrate and developability at the same time.

[0062] <Photosensitive alkali-soluble resin (B2-2)> The photosensitive alkali-soluble resin (B2-2) may have any polymerizable unsaturated group, but in this specification, it is preferable to use a resin synthesized by the following method (i) or (ii). In this way, the coating formed from the composition containing the resin is three-dimensionally crosslinked by photocuring, and the crosslink density is increased, thereby improving the chemical resistance.

[0063] [Method (i)] Method (i) is, for example, a method in which a polymer of an epoxy group-containing monomer and other monomers is first synthesized. Next, a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and a polybasic acid anhydride is reacted with the resulting hydroxyl group to obtain a photosensitive alkali-soluble resin. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

[0064] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0065] Examples of the monocarboxyl group-containing monomer 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.

[0066] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. The polybasic acid anhydride may have a carboxyl group that does not form an acid anhydride.

[0067] Examples of other monomers include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and 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.

[0068] Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide N-substituted maleimides such as N-phenylenediamine benzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide and 9-maleimidoacridine, 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, and PO-modified (meth)acrylate of nonylphenol.

[0069] As a method similar to the method (i), for example, there is a method in which a polymerizable unsaturated group and a carboxyl group are introduced by addition reaction of an epoxy group-containing monomer with a part of the side chain carboxyl groups of a copolymer obtained by copolymerizing a monocarboxyl group-containing monomer with another monomer.

[0070] [Method (ii)] In the method (ii), for example, a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to prepare a polymer, and then the hydroxyl group of the polymer is reacted with an isocyanate group of an isocyanate group-containing monomer to synthesize a photosensitive alkali-soluble resin.

[0071] Examples of the hydroxyl group-containing monomer include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of polyγ-valerolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, and glycerol mono(meth)acrylate is more preferred.

[0072] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate. Monomers that can be used other than the above-mentioned monomers include, in addition to the other monomers exemplified in the above method (i), phosphate ester group-containing monomers, etc.

[0073] The phosphate group-containing monomer is, for example, a compound obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0074] <Alkali-soluble resin (B2-1)> Examples of the alkali-soluble resin (B2-1) include an acrylic resin having an acidic group, an α-olefin / maleic acid (anhydride) copolymer, a styrene / styrenesulfonic acid copolymer, an ethylene / (meth)acrylic acid copolymer, or an isobutylene / maleic acid (anhydride) copolymer.

[0075] The binder resin (B2) can be used alone or in combination of two or more kinds.

[0076] The amount of the binder resin (B2) used is preferably from 1 to 50 parts by mass, and more preferably from 1 to 40 parts by mass, based on 100 parts by mass of the colorant (A).

[0077] <Polymerizable compound (C)> The polymerizable compound (C) is a monomer or oligomer containing a polymerizable unsaturated group. Examples of the polymerizable compound (C) include a compound (C1) having an alkylene oxide chain, an acid group-containing monomer, a urethane bond-containing monomer, and other monomers. Among these, the compound (C1) having an alkylene oxide chain with high polarity assists the orientation of the perfluoroalkyl group of the surfactant to the coating film surface. This reduces the dynamic surface tension of the coating film, and therefore, for example, coating unevenness can be suppressed during high-speed rotation of a spin coater.

[0078] <Compound (C1) Having an Alkylene Oxide Chain> Examples of the alkylene oxide chain of the compound (C1) having an alkylene oxide chain include a methylene oxide chain, an ethylene oxide (EO) chain, and a propylene oxide (PO) chain. Among these, an ethylene oxide chain is preferred in terms of hydrophilicity. The number of polymerizable unsaturated groups of the compound (C1) having an alkylene oxide chain is not particularly limited as long as the problem can be solved, but is preferably 2 to 6.

[0079] As preferred embodiments of the compound (C1) having an alkylene oxide chain, the compounds of the formulae (C1-1) to (C1-5) are exemplified below, although it goes without saying that the present invention is not limited to the following embodiments. [ka]

[0080] In (C1-1) and (C1-2), n represents an integer of 0 to 11. 1 each independently represents a hydrogen atom or a methyl group.

[0081] [ka] JPEG2025042662000004.jpg54149

[0082] In (C1-3) to (C1-5), n is an integer of 0 to 14 (however, all n's cannot be 0. m is an integer of 1 to 8. R and T may be the same or different.

[0083] Of these, the compound (C1) having an alkylene oxide chain is preferably the following compound. [ka] JPEG2025042662000006.jpg54142

[0084] Examples of the acid group-containing monomer 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.

[0085] (Urethane bond-containing monomer) Examples of the urethane bond-containing monomer include polyfunctional urethane acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting the alcohol with a (meth)acrylate having a hydroxyl group.

[0086] Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, trimethylolpropane EO modified tri(meth)acrylate, isocyanuric acid EO modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, Examples of the acrylic acid esters and methacrylic acid esters include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid ester of methylolated melamine, epoxy (meth)acrylate, and urethane acrylate, as well as (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.

[0087] The polymerizable compound (C) can be used alone or in combination of two or more kinds.

[0088] The blending amount of the polymerizable compound (C) is preferably 1 to 50 mass %, more preferably 2 to 40 mass parts, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is blended, the curability and developability are further improved.

[0089] [Photopolymerization initiator (D)] The photopolymerization initiator (D) is preferably an oxime ester photopolymerization initiator (D1). When an oxime ester compound absorbs ultraviolet light, the NO bond of the oxime is cleaved to generate an iminyl radical and an alkyloxy radical. These radicals are further decomposed to generate highly active radicals, so that a pattern can be formed with a small amount of exposure.

[0090] Examples of the oxime ester photopolymerization initiator (D1) include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.

[0091] Commercially available oxime ester photopolymerization initiators (D1) include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, and IRGACURE-OXE04 (all manufactured by BASF Japan Ltd.), TR-PBG-304, TR-PBG-305, TR-PBG-3057, TR-PBG-345, and TR-PBG-358 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.), ADEKA OPTOMER N-1919, ADEKA ARCLES NCI-730, NCI-831, and NCI-930 (manufactured by ADEKA Corporation).

[0092] Among these, the oxime ester photopolymerization initiator (D1) is preferably a compound having a carbazole skeleton, a fluorene skeleton, a diphenyl skeleton, or a dioxime having two oxime ester groups in the molecule. Examples of these compounds are shown below.

[0093] (Oxime ester photopolymerization initiator having a carbazole skeleton) The oxime ester photopolymerization initiator having a carbazole skeleton exemplified here is a compound having one oxime ester group. [ka] JPEG2025042662000008.jpg95138JPEG2025042662000009.jpg98143

[0094] Among these, the compounds (D1-1-3) to (D1-1-14) are preferable from the viewpoint of reactivity.

[0095] (Oxime ester photoinitiator with diphenyl skeleton) [ka]

[0096] Among these, compounds (D1-2-2) and (D1-2-4) are preferred in terms of photocurability.

[0097] (Fluorene skeleton-containing oxime ester photoinitiator) [ka]

[0098] Among these, the compound (D1-2-3) is preferred in terms of excellent solubility in organic solvents.

[0099] (Photopolymerization initiator with two oxime ester groups) [ka]

[0100] Among these, the compounds (D1-4-1) and (D1-4-2) are more preferable from the viewpoints of sensitivity, thermal stability and solubility.

[0101] As the photopolymerization initiator (D), a photopolymerization initiator other than the oxime ester-based photopolymerization initiator (D1) can be used. Other photopolymerization initiators include, 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;Examples of the compounds include phosphine-based compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone-based compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; and titanocene-based compounds.

[0102] The photopolymerization initiator (D) can be used alone or in combination of two or more kinds.

[0103] The content of the photopolymerization initiator (D) is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, and even more preferably 15 to 30 parts by mass, based on 100 parts by mass of the polymerizable compound (C) from the viewpoint of photocurability.

[0104] <Sensitizer> The photosensitive coloring composition may further contain a 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. , 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, or 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, 4,4'-bis(diethylamino)benzophenone, and the like. Among these, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, and the like are preferred.

[0105] The sensitizers can be used alone or in combination of two or more kinds.

[0106] The content of the sensitizer is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator. When an appropriate amount is contained, the curability and developability are further improved.

[0107] <Thiol-based chain transfer agent> The photosensitive coloring composition can contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. When the thiol-based chain transfer agent is used in combination with a photopolymerization initiator, a thiyl radical that is not easily inhibited by oxygen during radical polymerization after irradiation with light is generated, and the sensitivity of the photosensitive coloring composition is improved.

[0108] The thiol chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol chain transfer agent has four or more SH groups. As the number of functional groups increases, the coating becomes easier to photocure from the surface to the deepest part.

[0109] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, and ethylene glycol bisthiopropionate. Examples of the thiopropionate include erythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, and the like. Preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0110] The thiol chain transfer agents can be used alone or in combination of two or more kinds.

[0111] The content of the thiol chain transfer agent is preferably 0.1 to 10 mass%, more preferably 0.1 to 3 mass%, based on 100 mass% of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the photosensitivity and taper shape are improved, and wrinkles are less likely to occur on the coating surface.

[0112] <Polymerization inhibitor> The photosensitive coloring composition may contain a polymerization inhibitor, which can suppress photosensitivity due to diffracted light from a mask during exposure in a photolithography method, making it easier to obtain a pattern of a desired shape.

[0113] 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, and 2-n-butyl catechol. Examples of the alkyl resorcinol include alkyl resorcinol compounds such as ethylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucinone.

[0114] The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, a good pattern shape is easily obtained.

[0115] <Ultraviolet absorbing agent> The photosensitive coloring composition may contain an ultraviolet absorbing agent. Examples of the ultraviolet absorbing agent include benzotriazole-based compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds. The ultraviolet absorbing agent may be an oligomer or a polymer.

[0116] The content of the ultraviolet absorber is preferably 5 to 70% by mass relative to 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When an appropriate amount is contained, the resolution after development is further improved.

[0117] The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the adhesion between the substrate and the coating is further improved, and good resolution can be obtained.

[0118] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methylphenyl Mixture of benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side and straight chain alkyl esters with 95% methoxy-1-methylethyl acetate, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300 reaction products, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t- Butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0119] Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of the compound include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0120] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0121] Examples of the salicylate ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0122] <Antioxidants> The photosensitive coloring composition of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the photosensitive coloring composition from being oxidized and yellowed by the thermal process during thermal curing or ITO annealing, and therefore can improve the transmittance of the coating film. In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film crosslinking component is reduced, so that a highly sensitive crosslinking component is used or the amount of the photopolymerization initiator is increased, resulting in a phenomenon in which yellowing during the thermal process becomes stronger. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

[0123] Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In this specification, the antioxidant is preferably a compound that does not contain a halogen atom.

[0124] Among these, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0125] The antioxidants can be used alone or in combination of two or more kinds.

[0126] The content of the antioxidant is preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is used, the transmittance, spectral characteristics, and sensitivity are further improved.

[0127] <Surfactant (E)> The surfactant (E) contains a copolymer (E1) of a monomer (ED1) containing one or more selected from the group consisting of a fluorinated alkyl group and a poly(perfluoroalkylene ether) chain, and a monomer (ED2) having a bridged ring hydrocarbon (hereinafter referred to as copolymer (E1)). This reduces coating unevenness and striations, and allows the photosensitive coloring composition to be uniformly coated over the entire support. The bridged ring hydrocarbon is preferably an adamantyl ring, an isobornyl ring, or a dicyclopentanyl ring, and among these, an isobornyl ring is more preferable because it has a low Tg and can form a flexible coating film.

[0128] The fluorinated alkyl group-containing monomer is preferably, for example, a monomer represented by the following general formula (L1). [ka]

[0129] In the above general formula (L1), R represents a hydrogen atom or a methyl group, L represents any one of the groups represented by the following formulae (L-1) to (L-10), and Rf represents any one of the groups represented by the following formulae (Rf-1) to (Rf-7).

[0130] [ka]

[0131] In the above formulas (L-1) and (L-3) to (L-7), n represents an integer of 1 to 8. In the above formulas (L-8) to (L-10), m represents an integer of 1 to 8; Rf″ in the above formulae (L-6) and (L-7) represents any one of groups represented by the following formulae (Rf-1) to (Rf-7).

[0132] [ka]

[0133] In the above formulae (Rf-1) to (Rf-4), n is an integer of 1 to 6, and preferably 4 to 6. In the above formula (Rf-5), m is an integer of 1 to 18, n is an integer of 0 to 5, and the sum of m and n is 1 to 23. Preferably, m is an integer of 1 to 5, n is an integer of 0 to 4, and the sum of m and n is 4 to 5. In the above formula (Rf-6), m is an integer of 1 to 6, n is an integer of 1 to 3, l is an integer of 1 to 20, p is an integer of 0 to 5, and the sum of m, p, and the product of n and l is 2 to 71. Preferably, m is an integer of 1 to 3, n is an integer of 1 to 3, l is an integer of 1 to 6, p is an integer of 0 to 2, and the sum of m, p, and the product of n and l is 2 to 23. The fluoroalkyl group-containing monomer is preferably a monomer having the structure L-1, L-2, L-4 or L-5, more preferably a monomer having the structure L-1 or L-2. In addition, Rf" in the above formulae (L-6) and (L-7) is preferably (Rf-1).

[0134] Among the ethylenically unsaturated monomers (ED1) containing the fluorinated alkyl group, a thermally decomposable fluororesin exhibiting excellent smoothness can be obtained. This has the characteristic that the compatibility between the coating surface and the top coat is significantly improved by removing the fluorine-containing groups oriented on the surface by heat treatment, and therefore a monomer having a fluorinated alkyl group with 1 to 6 carbon atoms directly bonded to a fluorine atom is preferred, and a monomer having a fluorinated alkyl group with 4 to 6 carbon atoms directly bonded to a fluorine atom is more preferred.

[0135] The poly(perfluoroalkylene ether) chain-containing monomer may be a monomer having a structure in which a divalent carbon fluoride group having 1 to 3 carbon atoms and an oxygen atom are alternately linked. The divalent perfluoropolyether structure-containing group preferably has the following partial structure (X). (X) -(C g F 2g O) q - Here, g is an integer of 1 to 6, and q is an integer of 20 to 600, preferably 30 to 400, and more preferably 30 to 200.

[0136] The partial structure (X) is exemplified below. -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O- -CF2CF2CF2CF2O- CF2CF2CF2CF2CF2CF2O- -C(CF3)2O-

[0137] Among these, the following structure is more preferable: -CF2O- -CF2CF2O- -CF2CF2CF2O- -CF(CF3)CF2O- is preferred

[0138] The partial structure (X) may have one or more structures.

[0139] Examples of the monomer (ED2) having a bridged ring hydrocarbon include isobornyl acrylate, cyclopentadienyl acrylate, adamantyl acrylate, etc. Among these, isobornyl acrylate is preferred in terms of heat resistance and solvent resistance.

[0140] The copolymer (E1) is synthesized by polymerizing a monomer mixture containing the monomer (ED1) and the monomer (ED2). The polymerization is preferably solution polymerization. Examples of organic solvents used in solution polymerization include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, propylene glycol monomethyl ether acetate, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, diethyl ether, diisopropyl ether, tetrahydrofuran, dioxane, toluene, and xylene. Examples of polymerization initiators that can be used include peroxides such as benzoyl peroxide, and azo compounds such as azobisisobutyronitrile. Furthermore, chain transfer agents such as lauryl mercaptan, 2-mercaptoethanol, thioglycerol, ethylthioglycolic acid, and octylthioglycolic acid can be used as necessary.

[0141] The content of the surfactant (E) is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the coatability, pattern adhesion, transmittance, heat resistance, and solvent resistance of the photosensitive coloring composition are further improved.

[0142] The photosensitive coloring composition of the present invention may contain a fluorine-based surfactant (E2) other than the copolymer (E1) and other surfactants (E3).

[0143] (Other fluorosurfactants (E2)) Other fluorosurfactants (E2) are ethylene oxide adducts having a perfluoroalkyl group (perfluoroalkyl ethylene oxide compounds), and compounds having a perfluoroalkyl group but no bridged ring hydrocarbons. The structure of the perfluoroalkyl ethylene oxide compound is as follows: x F 2x+1 - (CH2) y -(OCH2CH2) zIt is represented by —OH. x represents the chain length of the perfluoroalkyl group and is usually 1 or more and 20 or less. y represents the chain length of the alkylene group and is usually 1 or more and 20 or less. z represents the number of ethylene oxide groups and is usually 1 or more and 50 or less.

[0144] Examples of surfactants which have a perfluoroalkyl group but do not have a bridged ring hydrocarbon include the following compounds. [ka]

[0145] (Other Surfactants (E3)) Examples of the other surfactants (E3) include silicone surfactants, acrylic surfactants, acetylene diol surfactants, etc. In terms of ionicity, examples of the surfactants include nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0146] Commercially available silicone surfactants include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie; DOWSIL Examples of the surfactants include FZ-7002, 2110, 2122, 2123, 2166, 2191, and 5609, X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-352A, KF-353A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341 manufactured by Shin-Etsu Chemical Co., Ltd., and TEGO WET250, 260, 270, and 280, and TEGO GLIDE410 and 450 manufactured by Evonik.

[0147] [Acrylic surfactant] Examples of the acrylic surfactant include a (meth)acrylic acid copolymer and a silicone surfactant.

[0148] Commercially available acrylic surfactants include, for example, BYK-350, 352, 354, 355, 358, 380, 381, and 392 manufactured by BYK-Chemie Co., Ltd., and Polyflow 57, 77, and 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0149] [Acetylene diol surfactant] Examples of acetylene diol surfactants include 2,4,7,9-tetramethyl-5-decyne-4,7-diol, 2,5,8,11-tetramethyl-6-dodecyne-5,8-diol, hexadec-8-yne-7,10-diol, 6,9-dimethyl-tetradec-7-yne-6,9-diol, 7,10-dimethylhexadec-8-yne-7,10-diol, and ethylene oxide and / or propylene oxide adducts thereof.

[0150] Commercially available acetylene diol surfactants include, for example, Surfynol 420, 440, 465, 485, SE, DF110D, DE85, and Olfine E1004 and 1010 manufactured by Nissin Chemical Industry Co., Ltd.

[0151] [Cationic Surfactant] Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0152] Commercially available cationic surfactants include, for example, Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate, manufactured by Kao Corporation.

[0153] [Anionic Surfactants] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenyletherdisulfonates, 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.

[0154] Examples of commercially available anionic surfactants 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.

[0155] [Ampholytic surfactants] Examples of amphoteric surfactants 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.

[0156] Commercially available amphoteric surfactants include, for example, Amphitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0157] [Nonionic surfactants] Examples of the nonionic surfactant include polyoxyethylene alkyl ethers, polyoxyethylene sorbitan fatty acid esters, glycerin fatty acid esters, and polyoxyethylene fatty acid esters.

[0158] Examples of commercially available nonionic surfactants include 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, and PP-290 manufactured by Kao Corporation, and Noigen XL-40, 50, and 60 manufactured by Daiichi Kogyo Seiyaku Co., Ltd.

[0159] <Storage stabilizer> The photosensitive coloring composition can contain a storage stabilizer. This improves the viscosity stability of the photosensitive 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-butyl pyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites.

[0160] The content of the storage stabilizer is preferably 0.1 to 10% by mass based on 100 parts by mass of the colorant (A).

[0161] <Silane coupling agent> Examples of the silane coupling agent include vinyl silanes such as vinyl trimethoxy silane and vinyl triethoxy silane, (meth)acrylic silanes such as 3-methacryloxypropyl methyl dimethoxy silane, 3-methacryloxypropyl trimethoxy silane, 3-methacryloxypropyl methyl diethoxy silane, 3-methacryloxypropyl triethoxy silane and 3-acryloxypropyl trimethoxy silane, epoxy silanes such as 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3-glycidoxypropyl methyl dimethoxy silane, 3-glycidoxypropyl trimethoxy silane, 3-glycidoxypropyl methyl diethoxy silane and 3-glycidoxypropyl triethoxy silane, N-2-(aminoethyl)-3-aminopropyl methyl dimethoxy silane, N-2- Examples of the silanes include aminosilanes such as (aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane.

[0162] The content of the silane coupling agent is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the colorant (A). When an appropriate amount is contained, the adhesion of the coating film formed from the photosensitive coloring composition is further improved, and the resolution of the pattern is also further improved.

[0163] <Solvent> The photosensitive coloring composition can contain a solvent. This makes it easier to adjust the viscosity of the photosensitive coloring composition, making it easier to form a coating with a smooth surface. The solvent may be appropriately selected according to the purpose of use, and may be contained in an appropriate amount.

[0164] Examples of the solvent include ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- or -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0165] Among these, in terms of coatability and drying property, solvents having a boiling point of 120° C. or more and 180° C. or less at 1 atm are preferred. For example, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are more preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are even more preferred.

[0166] The solvents can be used alone or in combination of two or more.

[0167] <Method for producing photosensitive composition> The photosensitive coloring composition is prepared by dispersing the colorant (A), resin (B), solvent, etc., to prepare a dispersion. Then, the resin (B), polymerizable compound (C), photopolymerization initiator (D), surfactant (E), etc. are mixed to prepare the photosensitive coloring composition. The timing of mixing each material is arbitrary. The dispersion process can also be carried out multiple times.

[0168] 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.

[0169] <Removal of large particles> The photosensitive coloring composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or a membrane filter, etc. In this way, it is preferable that the photosensitive coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

[0170] <Water content in photosensitive coloring composition> The photosensitive coloring composition of the present invention preferably has a water content (moisture content) of 2% by mass or less. When the water content is set to the above amount, the photosensitive coloring composition is less likely to lose dispersion stability and sensitivity even after storage over time. The water content is preferably 1.8% by mass or less, more preferably 1.6% by mass or less.

[0171] The method of controlling the water content is not particularly limited, and a known method is used. For example, a method of dehydrating the photosensitive coloring composition by adding molecular sieves during or after the production of the photosensitive coloring composition while blowing in a dry inert gas is included. Among them, the method of controlling the water content while blowing in a dry inert gas is preferred.

[0172] The water content can be measured by a known method such as the Karl Fischer method.

[0173] <Amount of toluene in the photosensitive coloring composition> The photosensitive coloring composition of the present invention may contain toluene. The content of toluene in the photosensitive coloring composition is preferably 0.1 to 10 ppm by mass. The upper limit of the toluene content is preferably 9 ppm by mass or less, more preferably 8 ppm by mass or less, and particularly preferably 7 ppm by mass or less. The lower limit is more preferably 0.2 ppm by mass or more, more preferably 0.3 ppm by mass or more, and particularly preferably 0.4 ppm by mass or more.

[0174] <Optical filters> The film of the present invention can be used for an optical filter. The optical filter can be used, for example, as a color filter which is a component of a liquid crystal display device, a solid-state imaging device, an organic EL display device, etc., or as an infrared cut filter or an infrared transmission filter which is a component of an infrared sensor, etc. <Color filters> The color filter of the present invention preferably has filter segments formed from a photosensitive coloring composition. The color filter of the present invention can include, for example, a red filter segment, a green filter segment, and a blue filter segment, and can also include a magenta filter segment, a cyan filter segment, and a yellow filter segment instead of or in addition to these.

[0175] <Manufacturing method of 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 in which a light-shielding agent is dispersed.

[0176] The color filter in this specification can be used for applications such as solid-state imaging devices, infrared sensors, organic EL displays, quantum dot displays, electronic paper, and head-mounted displays, in addition to liquid crystal displays.

[0177] <Liquid crystal display device> The liquid crystal display device of the present invention includes a color filter. The liquid crystal display device includes at least a color filter and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED, but in the present invention, it is preferable to use a white LED because it broadens the red reproduction range. Fig. 1 is a schematic cross-sectional view of a liquid crystal display device 10 including the color filter of the present invention. The device 10 shown in Fig. 1 includes a pair of transparent substrates 11 and 21 arranged to face each other with a space therebetween, and a liquid crystal LC is sealed between them.

[0178] A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. In addition, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0179] On the other hand, a color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. Red, green and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0180] A transparent protective film (not shown) is formed as necessary to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of the transparent protective film. An alignment layer 24 is provided to cover the transparent electrode layer 23.

[0181] In addition, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Below the polarizing plate 25, a backlight unit 30 is provided.

[0182] The liquid crystal LC is aligned according to a driving mode such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), OCB (Optically Compensated Birefringence), etc. A TFT (Thin Film Transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. In addition, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0183] On the other hand, a color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. Red, green and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0184] A transparent protective film (not shown) is formed as necessary to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of the transparent protective film. An alignment layer 24 is provided to cover the transparent electrode layer 23.

[0185] In addition, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Below the polarizing plate 25, a backlight unit 30 is provided.

[0186] The white LED light source may have a fluorescent filter formed on the surface of a blue LED, or a blue LED containing a phosphor in its resin package, and has a wavelength (λ3) in the range of 430 nm to 485 nm at which the emission intensity is maximized, a wavelength (λ4) in the range of 530 nm to 580 nm at which the emission intensity is maximized, and a wavelength (λ5) in the range of 600 nm to 650 nm at which the emission intensity is maximized, and the ratio (I4 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, Preferred is a white LED light source (LED1) having spectral characteristics in which the ratio (I5 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less, or a white LED light source (LED2) having a wavelength (λ1) at which the emission intensity is maximum within the range of 430 nm to 485 nm, a peak wavelength (λ2) of the second emission intensity within the range of 530 nm to 580 nm, and a ratio (I2 / I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 is 0.2 or more and 0.7 or less.

[0187] Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.).

[0188] Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D (manufactured by Nichia Chemical Industries, Ltd.).

[0189] <Solid-state imaging element> The solid-state imaging element of the present invention includes a color filter. The solid-state imaging element may have, for example, a substrate on which a plurality of photodiodes constituting a light receiving area of ​​the solid-state imaging element (such as a CCD image sensor, a CMOS image sensor, or an organic CMOS image sensor) and a light receiving element made of polysilicon or the like are provided, and the cured film of the present invention is provided on the side of the light receiving element forming surface or on the opposite side of the forming surface.

[0190] <Infrared sensor> The infrared sensor of the present invention includes a color filter. Fig. 2 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor. The infrared sensor 300 shown in Fig. 2 includes a light receiving element 310.

[0191] The imaging area provided on the light receiving element 310 is configured by combining an infrared absorbing filter 311 and a color filter 312 . The infrared absorbing filter 311 transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1300 nm). The color filter 312 is a color filter having pixels formed therein that transmit and absorb light of specific wavelengths in the visible light region, and for example, a color filter having red (R), green (G), and blue (B) pixels formed therein is used.

[0192] Between the infrared transmission filter 313 and the light receiving element 310, a resin film 314 that is capable of transmitting light of a wavelength that has passed through the infrared transmission filter 313 is disposed. The infrared transmission filter 313 is a filter that has a visible light shielding property and transmits infrared rays of a specific wavelength, and the cured film of the present invention containing the above-mentioned near infrared absorber (G) can be used. The infrared transmission filter 113 preferably shields light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1300 nm, for example.

[0193] A microlens 315 is disposed on the incident light side of the color filter 312 and the infrared transmission filter 313. A planarization film 316 is formed so as to cover the microlens 315.

[0194] In FIG. 2, the resin film 314 is disposed, but instead of the resin film 314, an infrared transmission filter 313 may be formed.

[0195] This infrared sensor can simultaneously capture image information, making it possible to perform motion sensing that recognizes the object whose movement is to be detected. In addition, this infrared sensor can obtain distance information, making it possible to capture images that include 3D information. Furthermore, this infrared sensor can also be used as a biometric authentication sensor.

[0196] The color filter of the present invention can also be used in applications such as quantum dot displays.

[0197] <Substrate, coating method, and pattern formation>

[0198] The substrate may be, for example, a substrate made of a material such as glass, resin, or silicon. An organic light-emitting layer may be formed on the substrate. An imaging element such as a CCD or CMOS may be formed on the substrate. If necessary, an undercoat layer may be provided on the substrate to improve adhesion with an upper layer, prevent diffusion of substances, and flatten the substrate surface.

[0199] The coating method may be a known method, such as a dropping method, a slit coating method, a spray method, a roll coating method, a rotary coating method, a casting coating method, an inkjet method, flexographic printing, screen printing, gravure printing, or offset printing.

[0200] The thickness of the membrane can be appropriately adjusted depending on the purpose, and is preferably 0.05 to 20.0 μm, more preferably 0.3 to 10.0 μm.

[0201] Next, a pattern is formed. Examples of a method for forming a pattern include a photolithography method and a dry etching method. When the film is used as a flat film, the step of forming a pattern is not necessary, and the film is dried as necessary after coating.

[0202] The method for forming the pattern will now be described in detail.

[0203] [Exposure process] When forming a pattern by photolithography, the coloring composition layer formed on the support is exposed to light in a pattern. For example, the coloring composition layer can be exposed to light in a pattern by using an exposure device such as a stepper through a mask having a predetermined mask pattern. This allows the exposed portion to be cured. As radiation (light) that can be used for exposure, ultraviolet rays such as g-rays and i-rays are preferably used (particularly preferably i-rays). The irradiation amount (exposure amount) is, for example, 0.03 to 2.5 J / cm. 2 is preferable, and 0.05 to 1.0 J / cm 2 is more preferred. The oxygen concentration during exposure can be appropriately selected. In addition to exposure in air, exposure may be performed in a low-oxygen atmosphere with an oxygen concentration of 19 volume% or less (e.g., 15 volume%, 5 volume%, or substantially oxygen-free), or in a high-oxygen atmosphere with an oxygen concentration of more than 21 volume% (e.g., 22 volume%, 30 volume%, or 50 volume%). The exposure illuminance can be appropriately set, and is usually 1000 W / m 2 ~100000W / m 2 (For example, 5000W / m 2 , 15000W / m 2 , 35000W / m 2 The oxygen concentration and exposure illuminance may be appropriately combined. For example, the oxygen concentration is 10% by volume and the illuminance is 10,000 W / m 2 , oxygen concentration 35% by volume, illuminance 20000W / m 2 etc.

[0204] [Development process] Next, an alkali development process is carried out, whereby the unexposed portions of the layer are dissolved in an aqueous alkali solution, and only the hardened portions remain, yielding a patterned film. Examples of alkaline developers include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, it suppresses roughening and peeling of the pattern and improves the remaining film rate after development. Examples of the developing method include a dipping method, a spraying method, a puddle method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0205] [Post-bake process] After development, a heat treatment (post-baking) can be carried out as necessary, which improves the resistance of the film. The temperature is preferably 80 to 300° C. The time is preferably about 2 minutes to 1 hour. When a material with low heat resistance is used for the substrate or when an organic electroluminescence element is used as the light source, the temperature is preferably 150° C. or less, and more preferably 130° C. or less. EXAMPLES

[0206] The present invention will be described below with reference to examples. However, the present invention is not limited to the examples. In the examples, "parts" means "parts by mass" and "%" means "% by mass".

[0207] Prior to the examples, the methods for measuring and calculating the average molecular weight of a resin and the acid value of a resin will be described.

[0208] <Average primary particle size of pigment> The average primary particle size of the pigment was measured by a common method of directly measuring the size of the primary particles from a transmission electron microscope (TEM) photograph. 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 size of the pigment particle. Next, for 100 or more pigment particles, the volume (weight) of each particle was calculated by approximating it to a rectangular parallelepiped of the calculated particle size, and the volume average particle size was taken as the average primary particle size.

[0209] (Dispersed particle size measurement) Using Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), particle permeability was set to absorption mode, particle shape to non-spherical, and D50 to mean particle size. The same solvents used for the dispersions were used as dilution solvents for the measurements, and measurements were taken on samples treated with ultrasonic waves immediately after sample preparation.

[0210] (Average molecular weight of resin) The number average molecular weight (Mn) and mass average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (manufactured by Tosoh Corporation), with two separation columns connected in series, and both packings were "TSK-GEL SUPER HZM-N" connected in series. The oven temperature was 40°C, THF solution was used as the eluent, and the flow rate was 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent, and 20 microliters were injected. All molecular weights are polystyrene equivalent values.

[0211] (Acid value of resin) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of resin solution, and the solution was stirred to dissolve uniformly. The solution was titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 mol / L KOH aqueous solution as the titrant, and the acid value (mgKOH / g) of the resin solution was measured. The acid value per unit of non-volatile content of the resin was calculated from the acid value of the resin solution and the concentration of non-volatile content of the resin solution.

[0212] (Amine value of basic resin type dispersant (mgKOH / g)) The amine value of the basic dispersion resin is the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 and converted into non-volatile content.

[0213] (Ammonium salt value (mgKOH / g)) The ammonium salt value is determined by titrating with 0.1N silver nitrate aqueous solution using 5% potassium chromate aqueous solution as an indicator, and then converted to the potassium hydroxide equivalent, and indicates the ammonium salt value of the non-volatile content.

[0214] <Preparation of fine pigment> <Fine particle size of colorant (A)> (Colorant (A-1)) 100 parts of CI Pigment Red 254 (BASF Japan "Irgaphor Red B-CF"), 10 parts of dye derivative (b-1), 1000 parts of ground salt, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 70° C. This mixture was added to 2000 parts of warm water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered and washed repeatedly with water to remove salt and solvent, and then dried at 80° C. for 24 hours to obtain colorant (A-1).

[0215] (Colorant (A-2)) 500 parts of CI Pigment Red 177 ("Chromophthal Red A2B" manufactured by BASF Japan Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 120° C. Next, this kneaded mixture was poured into 5 liters of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, which was then repeatedly filtered and washed with water to remove the sodium chloride and diethylene glycol, and then dried at 80° C. for one day to obtain colorant (A-2).

[0216] (Colorant (A-3)) 100 parts of CI Pigment Red 272 (BASF Japan "Irgazin (r) Flame Red K 3800"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) 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 colorant (A-3).

[0217] (Colorant (A-4)) 100 parts of CI Pigment Red 269 ("Toner Magenta F8B" manufactured by Clariant), 800 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 5 hours at 70° C. This mixture was poured into 4,000 parts of warm water, and stirred with a high-speed mixer for about 1 hour while heating to about 80° C. to form a slurry, which was filtered and washed repeatedly with water to remove the salt and solvent, and then dried at 80° C. for 24 hours to obtain colorant (A-4).

[0218] (Colorant (A-5)) 100 parts of 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) and kneaded for 6 hours at 70° C. This kneaded mixture was poured into 3000 parts of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove the sodium chloride and diethylene glycol, and then dried at 80° C. for a day and night to obtain 97 parts of colorant (A-5).

[0219] (Colorant (A-6)) 500 parts of CI Pigment Green 36 ("Leonol Green 6YK" manufactured by Toyo Color Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 4 hours at 120° C. Next, this kneaded mixture was poured into 5 liters of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, which was then filtered and repeatedly washed with water to remove the sodium chloride and diethylene glycol, and then dried at 80° C. for one day to obtain 490 parts of colorant (A-6).

[0220] (Colorant (A-7)) 500 parts of CI Pigment Green 63 ("OPTLION GREEN 8885" manufactured by Toyo Color Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 120°C for 4 hours. Next, this kneaded mixture was poured into 5 liters of warm water, heated to 70°C and stirred for 1 hour to form a slurry, which was then filtered and repeatedly washed with water to remove the sodium chloride and diethylene glycol, and then dried at 80°C for a day and night to obtain 490 parts of colorant (A-7).

[0221] (Colorant (A-8)) 100 parts of CI Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.), 1000 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 12 hours at 50° C. This mixture was poured into 3000 parts of warm water, heated to about 70° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which was filtered and washed repeatedly with water to remove the salt and solvent, and then dried at 80° C. for 24 hours to obtain colorant (A-8).

[0222] (Colorant (A-9)) 100 parts of CI Pigment Yellow 138 (BASF Japan "Paliotol Yellow K0961HD"), 800 parts of ground salt, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 4 hours at 70° C. This mixture was added to 3,000 parts of warm water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which was filtered and washed repeatedly to remove the salt and solvent, and then dried at 80° C. for 24 hours to obtain colorant (A-9).

[0223] (Colorant (A-10)) 100 parts of CI Pigment Yellow 139 (BASF 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 (Inoue Seisakusho Co., Ltd.) 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 form 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 colorant (A-10).

[0224] (Colorant (A-11)) 100 parts of CI Pigment Yellow 150 (Yellow Pigment E4GN manufactured by Lanxess), 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 for 10 hours at 60° C. Next, this mixture was poured into 3 liters of warm water, and stirred with a high-speed mixer for about 1 hour while heating to about 80° C. to form 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 colorant (A-11).

[0225] (Colorant (A-12)) 500 parts of 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 (Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 120° C. Next, this kneaded mixture was poured into 5 liters of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, which was then filtered and washed repeatedly to remove the sodium chloride and diethylene glycol, and then dried at 80° C. overnight to obtain colorant (A-12).

[0226] (Colorant (A-13)) 300 parts of a dioxazine-based purple pigment, Pigment Violet 23 ("Lionogen Violet RL" manufactured by Toyo Color Co., Ltd.) was added to 3000 parts of 96% sulfuric acid, stirred for 1 hour, and then poured into water at 5°C. After stirring for 1 hour, the mixture was filtered, washed with warm water until the washing liquid became neutral, and dried at 70°C. 120 parts of the obtained acid pasting-treated pigment, 5 parts of the dye derivative (b-2), 1500 parts of ground salt, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 20 hours. This mixture was added to 5000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, filtered, washed with water repeatedly to remove salt and solvent, and then dried at 80°C for 24 hours to obtain pigment (A-13).

[0227] (Dye solution (a-1~a-3)) (Resin 1 having cationic groups on the side chains) A four-necked separable flask equipped with a thermometer, stirrer, distillation tube, and condenser was charged with 67.3 parts of methyl ethyl ketone and heated to 75°C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were homogenized, then charged into a dropping funnel, attached to a four-necked separable flask, and dropped over 2 hours. Two hours after the end of the dropwise addition, it was confirmed from the non-volatile content that the polymerization yield was 98% or more and the weight average molecular weight (Mw) was 6830, and the mixture was cooled to 50°C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, and the mixture was reacted at 50°C for 2 hours, then heated to 80°C over 1 hour, and further reacted for 2 hours. In this way, resin 1 having cationic groups on the side chains having ammonium groups and a resin component of 47% by mass was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

[0228] (dye 1) 30 parts of resin 1 having a cationic group in the side chain in terms of non-volatile content was added to 2000 parts of water, thoroughly stirred and mixed, and then heated to 60°C. Meanwhile, an aqueous solution was prepared by dissolving 10 parts of CI Acid Red 52 in 90 parts of water, and the solution was gradually dropped into the resin solution. After the dropwise addition, the solution was stirred at 60°C for 120 minutes to thoroughly react. To confirm the end point of the reaction, the reaction solution was dropped onto a filter paper, and the end point was determined to be when no bleeding occurred, and the salt-forming compound was obtained. After cooling to room temperature while stirring, suction filtration was performed, and the salt-forming compound remaining on the filter paper was dried by removing moisture in a dryer to obtain a colorant (dye 1) which is a salt-forming compound of CI Acid Red 52 and resin 1 having a cationic group in the side chain. At this time, the content of the active colorant component derived from CI Acid Red 52 in the colorant (dye 1) was 25% by mass.

[0229] (dye 2) A colorant (dye 2), which is a salt-forming compound of CI Acid Red 289 and resin 1 having a cationic group on its side chain, was obtained in the same manner as in the production of colorant (dye 1), except that CI Acid Red 52 was changed to CI Acid Red 289. At this time, the content of the active colorant component derived from CI Acid Red 289 in the colorant (dye 2) was 27% by mass.

[0230] (dye 3) In a 1L stainless steel reaction vessel equipped with a reflux condenser, 5.0 parts of CI Basic Violet 10 (BV10: Taoka Chemical Co., Ltd.: Rodamine B) and 1.6 parts of hydroxyethyl methacrylate (HEMA) were dissolved in 40 ml of dichloromethane under a nitrogen atmosphere, and 2.2 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 0.25 parts of dimethylaminopyridine were added and stirred at room temperature for 24 hours. The resulting dichloromethane solution was washed with water and dried under reduced pressure, and then purified with a silica gel column to obtain a colorant (dye 3).

[0231] (Preparation of dye solution (a-1)) The following mixture was stirred and mixed to be homogeneous, and then filtered through a filter having a pore size of 5.0 μm to prepare a colored composition (dye solution (a-1)). Colorant (dye 1) 12.5 parts Propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc) 87.5 parts

[0232] (Preparation of dye solutions (a-2) and (a-3)) In the same manner as for the dye solution (a-1), dye solutions (a-2) and (a-3) were prepared using dye 2 and dye 3, respectively.

[0233] (Dye derivative (b)) The dye derivatives (b-1 to b-7) used are shown below.

[0234] (dye derivative b-1) [ka]

[0235] (dye derivative b-2) [ka]

[0236] (dye derivative b-3) [ka]

[0237] (dye derivative b-4) [ka]

[0238] (dye derivative b-5) [ka]

[0239] (dye derivative b-6) [ka]

[0240] (dye derivative b-7) [ka]

[0241] (Production Example 1 Acidic Resin-Type Dispersant (B1-1)) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 50.0 parts of methyl methacrylate and 50.0 parts of 2-methoxyethyl acrylate were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 45.4 parts of PGMAc was added to 6.0 parts of 3-mercapto-1,2-propanediol, and reacted for 10 hours. It was confirmed that 95% or more had reacted by measuring the non-volatile content. At this time, the weight average molecular weight was 4000. Next, 9.7 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 31.7 parts of PGMAc, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 120°C for 7 hours. It was confirmed that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and the reaction was terminated. After the reaction was completed, PGMAc was added so that the nonvolatile content became 60% by weight, and a solution of an acidic resin-type dispersant (B1-1) having an acid value of 43 mgKOH / g and a weight average molecular weight of 9,500 was obtained.

[0242] (Production Example 2 Acidic Resin-Type Dispersant (B1-2) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 parts of monobutyltin (IV) oxide as a catalyst were charged, and the mixture was replaced with nitrogen gas, and then heated and stirred at 120 ° C for 4 hours. After confirming that 98% had reacted by measuring the non-volatile content, 73.3 parts of pyromellitic anhydride were added and reacted at 120 ° C for 2 hours. The reaction was terminated when it was confirmed that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. An acidic resin-type dispersant (B1-2) solution with a non-volatile content of 40% was obtained by adjusting the non-volatile content with PGMAc. The obtained dispersant was a white solid at room temperature and had an acid value of 49 mg KOH / g.

[0243] (Production Example 3 Acidic Resin-Type Dispersant (B1-3)) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged, and after replacing with nitrogen gas, the reaction was carried out at 120 ° C. for 5 hours (first step). It was confirmed that 95% or more of the acid anhydride was half-esterified by measuring the acid value. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, and the reaction vessel was heated to 80 ° C., and 1.2 parts of 2,2'-azobis (2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours (second step). It was confirmed by measuring the non-volatile content that 95% or more had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were charged, and the reaction was carried out until the disappearance of the peak at 2270 cm-1 due to the isocyanate group was confirmed by IR (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and the non-volatile content was adjusted with PGMAc to obtain an acidic resin-type resin-type dispersant (B1-3) solution containing a (meth)acryloyl group, which is an ultraviolet crosslinking group, with a non-volatile content of 40%. The acid value of the obtained acidic resin-type dispersant was 68 gKOH / g, the unsaturated double bond equivalent was 1593 g / mol, and the weight average molecular weight was 13,000.

[0244] (Production Example 4 Acidic Resin-Type Dispersant (B1-4)) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 50.0 parts of t-butyl acrylate, 45.0 parts of methyl methacrylate, and 5.0 parts of methacrylic acid were charged and replaced with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 70.7 parts of PGMAc was added to 6.0 parts of 3-mercapto-1,2-propanediol, and reacted for 10 hours. It was confirmed that more than 95% had reacted by measuring the non-volatile content. Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 38.0 parts of PGMAc, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120 ° C. for 5 hours. Then, 12.1 g of 3-methoxybutanol was added, and the mixture was reacted at 120 ° C. for 3 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After the reaction was completed, PGMAc was added to prepare a non-volatile content of 40% by mass, and a solution of an acidic resin-type dispersant (B1-4) having an acid value of 110 mg KOH / g and a weight average molecular weight of 9000 was obtained.

[0245] (Production Example 5 Acidic Resin-Type Dispersant (B1-5)) A reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer was charged with 20.0 parts of t-butyl acrylate, 45.0 parts of methyl methacrylate, 30.0 parts of ethyl acrylate, and 5.0 parts of methacrylic acid, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 70.7 parts of PGMAc was added to 6.0 parts of 3-mercapto-1,2-propanediol, and the reaction was carried out for 10 hours. It was confirmed that more than 95% had reacted by measuring the non-volatile content. Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 38.0 parts of PGMAc, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120 ° C. for 5 hours. Then, 12.1 g of 3-methoxybutanol was added, and the mixture was reacted at 120 ° C. for 3 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. After the reaction was completed, PGMAc was added to prepare a non-volatile content of 40% by mass, and a solution of an acidic resin-type dispersant (B1-5) having an acid value of 105 mg KOH / g and a weight average molecular weight of 9400 was obtained.

[0246] (Production Example 6 Acidic Resin-Type Dispersant (B1-6)) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), and 70.8 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100°C and reacted for 5 hours. Then, 12.1 g of 3-methoxybutanol was added and reacted at 120°C for 3 hours. After confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, the temperature in the system was cooled to 70°C, 50.0 parts of t-butyl acrylate and 50.0 parts of methyl methacrylate were charged, and 38.0 parts of PGMAc in which 0.1 parts of 2,2'-azobisisobutyronitrile had been dissolved was added and reacted for 10 hours. The reaction was terminated when it was confirmed that the polymerization had progressed to 95% or more by measuring the non-volatile content. After the reaction was completed, PGMAc was added so that the non-volatile content became 40% by mass, and a solution of an acidic resin-type dispersant (B1-6) having an acid value of 93 mgKOH / g and a weight average molecular weight of 10,800 was obtained.

[0247] <Production example of binder resin (B2)> (Production Example 12 Binder resin (B2-1-1) liquid) 150 parts of cyclohexanone was placed in a reaction vessel, and the vessel was heated to 80°C while nitrogen gas was injected into the vessel. At the same temperature, a mixture of 20.0 parts of methacrylic acid, 10.0 parts of methyl methacrylate, 55.0 parts of hydroxyethyl methacrylate, and 15.0 parts of azobisisobutyronitrile was added dropwise over 1 hour to carry out a polymerization reaction. After the addition, the mixture was reacted at 80°C for another 3 hours, and then 1.0 parts of azobisisobutyronitrile was dissolved in 50 parts of cyclohexanone and added. The reaction was continued for another 1 hour at 80°C and cooled to room temperature. Approximately 2 g of the resin solution was sampled and dried at 180°C for 20 minutes to measure the non-volatile content, and cyclohexanone was added so that the non-volatile content was 30% by weight to prepare a binder resin (B2-1-1) liquid. The weight average molecular weight of the binder resin was 40,000.

[0248] (Production Example 13 Binder resin (B2-1-2) liquid) A separable 4-neck flask was fitted with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer. 190 parts of PGMAc was charged into the reaction vessel, which was then heated to 80°C. The atmosphere in the reaction vessel was replaced with nitrogen, and a mixture of 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd.'s "Aronix M110") and 1.1 parts of 2,2'-azobisisobutyronitrile was dropped into the reaction vessel over a period of 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried at 180°C for 20 minutes to measure the non-volatile content, and PGMAc was added to the resin solution previously synthesized so that the non-volatile content was 30% to prepare a binder resin (B2-1-2) liquid. The weight average molecular weight (Mw) was 26,000.

[0249] (Production Example 14 Binder resin (B2-2-1) liquid) 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 in the reaction vessel, which was then heated to 80°C and substituted with nitrogen in the reaction vessel. From the dropping tube, a mixture of 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropping was completed, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the nitrogen gas was stopped and the whole amount of the copolymer solution was stirred while injecting dry air for 1 hour, and then cooled to room temperature. Then, a mixture of 6.5 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 added dropwise at 70 ° C. for 3 hours. After the dropwise addition, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone was added to the resin solution synthesized earlier so that the non-volatile content was 30% to prepare a binder resin (B2-2-1). The weight average molecular weight (Mw) was 18,000.

[0250] (Production Example 15 Binder Resin (B2-2-2) Liquid) A separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer was charged with 170 parts of cyclohexanone, heated to 80°C, and the flask was replaced with nitrogen. From the dropping tube, a mixture of 18 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate and 2.0 parts of 2,2'-azobisisobutyronitrile was dropped over 2 hours. After the dropping, the mixture was further reacted at 100°C for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was continued at 100°C for 1 hour. Next, the inside of the container was replaced with air, and 9.3 parts of acrylic acid (corresponding to 100 mol% of glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 parts of hydroquinone were added to the container, and the reaction was continued for 6 hours at 120 ° C., and the reaction was terminated when the non-volatile acid value reached 0.5, to obtain an acrylic resin solution. Furthermore, 19.5 parts of tetrahydrophthalic anhydride (corresponding to 100 mol% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and PGMAc was added to the resin solution synthesized earlier so that the non-volatile content was 30 mass% to prepare a binder resin (B2-2-2) liquid. The weight average molecular weight (Mw) was The number was 19,000.

[0251] <Preparation of surfactant (E) solution> (Production of surfactant (E1-1) solution) In a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirrer, 111 parts of methyl ethyl ketone as a solvent, 47 parts of isobornyl methacrylate as a monomer having a bridged ring hydrocarbon, and 25 parts of 2-(nonafluorohexyl)ethyl acrylate as a monomer containing a fluorinated alkyl group were charged, and the mixture was heated to 60°C while stirring under a nitrogen stream. Next, 4 parts of 2,2'-bipyridyl, 1.5 parts of cuprous chloride and 2.1 parts of ethyl 2-bromoisobutyrate were added, and the mixture was reacted at 60°C for 35 hours under a nitrogen stream. Next, 30 parts of activated alumina was added to the resulting reaction product and stirred. After filtering the activated alumina, the solvent was distilled off under reduced pressure to obtain a copolymer of a monomer containing a fluorinated alkyl group and a monomer having an isobornyl group. After cooling to room temperature, two portions of the copolymer of the monomer containing a fluorinated alkyl group and the monomer having an isobornyl group were sampled and dried by heating at 180°C for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether acetate was added to the fluorine-containing resin solution so that the non-volatile content became 1 mass %, to prepare a surfactant (E1-1) solution.

[0252] (Preparation of surfactant (E1-2 and E1-3) solutions) Solutions of surfactants (E1-2) and (E1-3) were prepared in the same manner as for surfactant (E1-1), except that the monomer used in the synthesis of surfactant (E1-1) was changed to the monomer shown in Table 1. The surfactants (E1-1 to E1-3) are shown in Table 1. [Table 1]

[0253] <Method of producing colored composition> [Production Example 1] (Preparation of Coloring Composition (X-1)) The mixture below was stirred and mixed to make it uniform, and then dispersed for 3 hours in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a filter with a pore size of 5.0 μm to produce a colored composition (X-1) with a non-volatile content of 20.0% by mass. Pigment (A-1): 15.0 parts Pigment derivative (b-1): 1.0 part Resin solution (B1-1): 10.0 parts PGMAc: 74.0 copies

[0254] [Manufacturing Examples 2-39] (Preparation of Colored Compositions (X-2 to X-39)) Colored compositions (X-2 to X-39) were prepared in the same manner as in Production Example 1, except that the blending in Production Example 1 was changed to the material types and masses shown in Table 2.

[0255] [Table 2]

[0256] <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 having a pore size of 0.2 μm to obtain a photosensitive coloring composition (X-1). Coloring composition (X-1): 36.4 parts Coloring composition (X-30): 11.6 parts Binder resin (B2-1-1): 5.0 parts Polymerizable compound (C1-1): 1.2 parts Photopolymerization initiator (D1-A): 0.3 parts Surfactant (E1-1): 2.5 parts Thermosetting compound (F-1): 1.0 part Thermosetting compound (F-2): 1.0 part Sensitizer (G): 0.1 parts Thiol chain transfer agent (H): 0.1 parts Polymerization inhibitor (I): 0.01 part Ultraviolet absorber (J): 0.1 parts Antioxidant (K): 0.1 parts Storage stabilizer (L): 0.1 part Adhesion improver (M): 0.1 part Solvent (S): 40.39 parts

[0257] [Examples 2 to 84, Comparative Examples 1 to 8] (Photosensitive coloring composition (Y-2~Y-92)) The coloring composition of Example 1 and the resin (B), the polymerizable compound (C), the photopolymerization initiator (D), and the type of the fluorine-based compound (E) were changed as shown in Tables 3 to 12, and the same procedure as in Example 1 was carried out to prepare photosensitive coloring compositions (Y-2 to Y-92).

[0258] In the table, *1 indicates the total amount of thermosetting compound (F-1), thermosetting compound (F-2), sensitizer (G), thiol chain transfer agent (H), polymerization inhibitor (I), UV absorber (J), antioxidant (K), storage stabilizer (L), and adhesion improver (M). *2 is the colorant content in the non-volatile matter of the photosensitive coloring composition. *3 is the polymerizable compound content in the non-volatile matter of the photosensitive coloring composition. The raw materials in the table are as follows:

[0259] (C1-1) Tripropylene glycol diglycidyl ether-acrylic acid adduct [Epoxy ester 200PA(N) (Kyoeisha Chemical Co., Ltd.)] [ka]

[0260] (C1-2) Propylene glycol diglycidyl ether-acrylic acid adduct [Epoxy ester 70PA(N) (Kyoeisha Chemical Co., Ltd.)] [ka]

[0261] (C1-3) Trimethylolpropane EO modified triacrylate [Aronix M-350 (manufactured by Toagosei)] [ka]

[0262] (C1-4) EO modified dipentaerythritol hexaacrylate [KAYARAD DPEA-12 (manufactured by Nippon Kayaku)] [ka]

[0263] (C1-5) Mixture of EO-modified isocyanuric acid diacrylate and EO-modified isocyanuric acid triacrylate [Aronix M-315 (manufactured by Toagosei)] [ka]

[0264] (C2) Dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [Aronix M402 (manufactured by Toagosei)]

[0265] <Photopolymerization initiator (D)> (D-1) 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Omnirad 907 (IGM Resins)] (D-2) 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Omnirad 379EG (IGM Resins)] (D-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [Omnirad TPO (manufactured by IGM Resins)] (D-4) 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole [Biimidazole (Kurokane Chemicals)] (D-5) p-Dimethylaminoacetophenone [DMA (manufactured by Daikifine)] (D-6) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime) [Omnirad 2959 (IGM Resins)] (D-7) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Omnirad 819 (IGM Resins)] The above (D-1) to (D-7) were mixed in equal amounts to prepare a photopolymerization initiator (DM). (D1-A) A mixture of equal amounts of the four oxime ester photoinitiators shown below. [ka] (D1-B) Shown in the following formula (1). Formula (1) [ka] (D1-C) A mixture of equal amounts of three types of photopolymerization initiators shown in the following formula (2): Formula (2) [ka] (D1-D) A photopolymerization initiator represented by the following formula (3): Formula (3) [ka] (D1-E) A photopolymerization initiator represented by the following formula (4): Formula (4) [ka] (D1-F) A photopolymerization initiator represented by the following formula (5): Formula (5) [ka] (D1-G) A photopolymerization initiator represented by the following formula (6): Formula (6) [ka] (D1-H) A photopolymerization initiator represented by the following formula (7): Formula (7) [ka] (D1-I) A photopolymerization initiator represented by the following formula (8): Formula (8) [ka]

[0266] (Surfactant (E2) solution) (E2) A solution in which 1 part of perfluorooctanoic acid is dissolved in 99 parts of PGMAc. (Surfactant (E3-1) solution) (E3-1) A solution in which 1 part of BYK-330 manufactured by BYK-Chemie was dissolved in 99 parts of PGMAc. (E3-2) A solution in which 1 part of Kao Corporation's "Emulgen 103" was dissolved in 99 parts of PGMAc.

[0267] <Thermosetting compound (F)> ·Thermosetting compound (F-1) (F-1-1) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol [EHPE-3150 (manufactured by Daicel)], (F-1-2) Glycidyl etherified epoxy compounds of sorbitol [Denacol EX611 (Nagase ChemteX)] (F-1-3) Triglycidyl isocyanurate Equal amounts of (F-1-1) to (F-1-3) were mixed together to prepare a thermosetting compound (F-1). ·Thermosetting compound (F-2): 3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane [Aron Oxetane OXT-221 (manufactured by Toagosei)]

[0268] <Sensitizer (G)> (G-1) 2,4-Diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku)] (G-2) 4,4'-bis(diethylamino)benzophenone [CHEMARK DEABP (manufactured by Chemark Chemical)] The above (F-1) and (F-2) were mixed in equal amounts to prepare sensitizer (G).

[0269] <Thiol-based chain transfer agent (H)> (H-1) Trimethylolethane tris(3-mercaptobutyrate) [TEMB (Showa Denko)] (H-2) Trimethylolpropane tris(3-mercaptobutyrate) [TPMB (Showa Denko)] (H-3) Pentaerythritol tetrakis(3-mercaptopropionate) [PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (H-4) Trimethylolpropane tris(3-mercaptopropionate) [TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (H-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)] The above (H-1) to (H-5) were mixed in equal amounts to prepare a thiol-based chain transfer agent (G).

[0270] <Polymerization inhibitor (I)> (I-1) 3-Methylcatechol (I-2) Methylhydroquinone (I-3) tert-Butylhydroquinone The above (I-1) to (I-3) were mixed in equal amounts to prepare a polymerization inhibitor (I).

[0271] <Ultraviolet absorber (J)> (J-1) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine [TINUVIN400 (BASF Japan)] (J-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN900 (BASF Japan)] The above (J-1) and (J-2) were mixed in equal amounts to prepare an ultraviolet absorber (J).

[0272] <Antioxidant (K)> (K-1) Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (K-2) Dioctadecyl 3,3'-thiodipropanoate (K-3) Tris[2,4-di-(t)-butylphenyl]phosphine (K-4) Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (K-5) p-Octylphenyl Salicylate The above (K-1) to (K-5) were mixed in equal amounts to prepare an antioxidant (K).

[0273] <Storage stabilizer (L)> (L-1) 2,6-bis(1,1-dimethylethyl)-4-methylphenol ("BHT" manufactured by Honshu Chemical Industry Co., Ltd.) (L-2) Triphenylphosphine ("TPP" manufactured by Hokko Chemical Industry Co., Ltd.) The above (L-1) and (L-2) were mixed in equal amounts to prepare a storage stabilizer (L).

[0274] <Adhesion improver (M)> (M-1) "KBM-5103 (Shin-Etsu Chemical Co., Ltd.)" (M-2) 3-Glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (Shin-Etsu Chemical Co., Ltd.)] (M-3) 3-Methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (Shin-Etsu Chemical Co., Ltd.)] (M-4) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (Shin-Etsu Chemical Co., Ltd.)] (M-5) 3-Mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (Shin-Etsu Chemical Co., Ltd.)] The above (M-1) to (M-5) were mixed in equal amounts to prepare an adhesion improver (M).

[0275] <Solvent (S)> The solvent (SM) is a mixture of the following (S-1) to (S-6) in the parts by mass shown below. (S-1) PGMAc (boiling point 146℃) 20 parts (S-2) Cyclohexanone (boiling point 155°C) 20 parts (S-3) Ethyl 3-ethoxypropionate (boiling point 169°C) 20 parts (S-4) Propylene glycol monomethyl ether (boiling point 121°C) 20 parts (S-5) Cyclohexanol acetate (boiling point 172°C) 10 parts (S-6) Dipropylene glycol methyl ether acetate (boiling point 188°C) 10 parts

[0276] <Evaluation of Photosensitive Coloring Composition> The obtained photosensitive coloring compositions (Y-1 to 79) were evaluated by the following methods, and the results are shown in Tables 3-1 to 3-8. Each test was carried out according to the following method. The test results are shown in Table 4. The meanings of the evaluation ranks are as follows: ◎: Very good 〇: Good △: Practical ×: Not suitable for practical use

[0277] <Formation of filter segments> The obtained photosensitive coloring composition was applied by a spin coater onto a glass substrate having a length of 100 mm, width of 100 mm, and thickness of 0.7 mm on which a black matrix had been formed, so that the dry film thickness was 2.4 μm, and the coating was dried at a temperature of 90° C. for 90 seconds to obtain a coating film. Next, the obtained coating film was irradiated with 100 mJ / cm using an ultra-high pressure mercury lamp through a photomask having a predetermined pattern. 2 The coated film was irradiated with ultraviolet light of 1000 nm, and then spray-developed with an alkaline developer consisting of a 0.2% by mass aqueous solution of sodium carbonate to remove the uncured portions and form the desired pattern. The coated film was then heated in an oven at 230°C for 20 minutes to form a filter segment. The thickness of the coating film was measured using a Dektak3030 (manufactured by Japan Vacuum Engineering Co., Ltd.).

[0278] <Evaluation of striations and coating unevenness> A square pattern of 50 μm in length and width and 0.8 μm in height was formed in a range of 2000 μm in length × 3000 μm in width on the entire surface of a silicon wafer with a diameter of 8 inches (1 inch = 2.54 cm) by etching. Each pattern was separated by a groove with a width of 2.5 μm. Next, the obtained photosensitive coloring composition was applied by spin coating to form a film with a dry thickness of 1.0 μm, and then heated at 100 ° C. for 120 seconds using a hot plate. Then, it was further heated at 200 ° C. for 300 seconds using a hot plate. After cooling to room temperature, steps located at 1 to 28 positions on the silicon wafer shown in FIG. 3 were selected, and the corners of the steps were observed with an optical microscope (50 times). Of the four corners of the step, the corner farthest from the center of the silicon wafer was observed, and the striations and coating unevenness were evaluated according to the following criteria. (Evaluation of striations) ◎: No striations were observed in any of the sites 1 to 28 in FIG. △: Striations were observed in less than 10 of the sites 1 to 28 in FIG. 3. ×: Striations were observed in 10 or more of the sites 1 to 28 in FIG.

[0279] (Evaluation of coating unevenness) ⊚: No coating unevenness was observed in any of the areas 1 to 28 in FIG. Δ: Coating unevenness was observed in less than 10 of the sites 1 to 28 in FIG. ×: Coating unevenness was observed in 10 or more of the sites 1 to 28 in FIG.

[0280] (Heat resistance evaluation) The obtained photosensitive coloring composition was applied to a glass substrate having a length of 100 mm, width of 100 mm, and thickness of 1.1 mm using a spin coater so that the dry film thickness was 2.0 μm, and then dried at 70 ° C for 20 minutes. The coating film was then heated at 230 ° C for 60 minutes and allowed to cool to room temperature to produce a coating film substrate (one embodiment of a color filter). The chromaticity ([L * (1), a * (1), b * (1)]) of the obtained coating film under a C light source was measured using a microspectrophotometer (Olympus Optical Co., Ltd. "OSP-SP100"). Thereafter, the coating film substrate was heated at 250 ° C for 1 hour as a heat resistance test, and the chromaticity ([L * (2), a * (2), b * (2)]) under a C light source was measured, and the color difference ΔEab * was calculated using the following formula and evaluated on the following four levels. ΔEab*=√((L*(2)-L*(1))2+(a*(2)-a*(1))2+(b*(2)-b*(1))2) ◎: ΔEab* is less than 1.0 (very good) ◯: ΔEab* is 1.0 or more and less than 2.5 (good) △: ΔEab* is 2.5 or more and less than 5.0 (practical) ×: ΔEab* is 5.0 or more (extremely poor)

[0281] [Table 3]

[0282] [Table 4]

[0283] [Table 5]

[0284] [Table 6]

[0285] [Table 7]

[0286] [Table 8]

[0287] [Table 9]

[0288] [Table 10]

[0289] [Table 11]

[0290] [Table 12] [Explanation of symbols]

[0291] 10 LCD display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color Filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing Plate 30 Backlight unit 31 White LED light source LC Liquid Crystal 300 Infrared Sensor 310 Photodetector 311 Infrared absorbing filter 312 Color Filter 313 Infrared absorbing transmission filter 314 Resin Film 315 Micro Lens 316 Flat membrane

Claims

1. A photosensitive coloring composition comprising a colorant (A), a resin (B), a polymerizable compound (C), a photopolymerization initiator (D) and a surfactant (E), the polymerizable compound (C) contains a compound (C1) having an alkylene oxide chain, A photosensitive coloring composition, characterized in that the surfactant (E) comprises a copolymer (E1) of a monomer (ED1) containing one or more selected from the group consisting of a fluorinated alkyl group and a poly(perfluoroalkylene ether) chain, and a monomer (ED2) having a bridged ring hydrocarbon.

2. 2. The photosensitive coloring composition according to claim 1, wherein the bridged ring hydrocarbon is an adamantyl ring, an isobornyl ring or a dicyclopentanyl ring.

3. The photosensitive coloring composition according to claim 1, wherein the content of the colorant (A) is 30 to 70 mass%, and the content of the polymerizable compound (C) is 0.1 to 20.0 mass%, based on 100 mass% of the nonvolatile content of the photosensitive coloring composition.

4. 2. The photosensitive coloring composition according to claim 1, wherein the photopolymerization initiator (D) comprises a photopolymerization initiator (D1) having an oxime ester skeleton.

5. A color filter having filter segments formed from the photosensitive coloring composition according to any one of claims 1 to 4.

6. A solid-state imaging device comprising the color filter according to claim 5.

7. A liquid crystal display device comprising the color filter according to claim 5.

8. An infrared sensor comprising the color filter according to claim 5 .

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