Coloring composition, photosensitive coloring composition, color filter, and liquid crystal display device using the same

Abstract

To provide a coloring composition which is reduced in occurrence of a foreign matter, is excellent in a pattern shape and has a high development speed while having high colorant concentration, and a color filter and a liquid crystal display device using the same.SOLUTION: A coloring composition contains an organic pigment (A), a resin type dispersant (C) and a binder resin (C), in which the organic pigment (A) contains one or more selected from a zinc phthalocyanine pigment (A1) and an aluminum phthalocyanine pigment (A2), the resin type dispersant (B) contains a basic resin type dispersant (B1), the binder resin (C) contains a copolymer of a monomer (CL) having a homopolymer having a glass transition temperature of lower than 0°C and a monomer (CH) having a homopolymer having a glass transition temperature of 150°C or higher, and in the total monomer, the monomer (CL) is 1-99 mass% and the monomer (CH) is 1-50 mass%.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a coloring composition and a photosensitive coloring composition used for manufacturing a color filter used in a color liquid crystal display device, a color solid-state imaging device, an organic EL display device, a quantum dot display device, and electronic paper, and a color filter and a liquid crystal display device including a filter segment formed using the same. A color filter is composed of fine stripe-shaped filter segments of two or more different hues arranged parallel or crossing on the surface of a transparent substrate such as glass, or fine filter segments arranged in a fixed vertical and horizontal array. The filter segments are fine, ranging from several microns to several hundred microns, and are arranged in a regular array for each hue. In general, in a color liquid crystal display device, a transparent electrode for driving the liquid crystal is formed on the color filter by deposition or sputtering, and an alignment film for aligning the liquid crystal in a fixed direction is formed on the transparent electrode. In order to obtain sufficient performance of these transparent electrodes and alignment films, their formation must be performed at a high temperature of generally 200° C. or higher, preferably 230° C. or higher.

[0002] For this reason, currently, the predominant method for producing color filters is a method called a pigment dispersion method, in which a pigment having excellent light resistance and heat resistance is used as a coloring material. In the case of the pigment dispersion method, a photosensitive coloring composition (pigment resist) in which a pigment is dispersed in a photosensitive resin solution is applied to a transparent substrate such as glass, the solvent is removed by drying, and then a pattern of one filter color is exposed to light. The unexposed areas are then removed in a development process to form a pattern of the first color, and a treatment such as heating is added as necessary. The same operation is then repeated sequentially for all filter colors to produce a color filter.

[0003] In recent years, color LCD devices have come to form a large market for LCD color televisions, car navigation systems, and notebook computers with integrated LCD devices, and are also beginning to spread as monitors and televisions for desktop computers, taking advantage of their energy-saving and space-saving features. LCD devices are attracting attention as display devices to replace conventional CRTs, but the color reproduction characteristics of LCD devices are currently inferior to those of CRTs. Therefore, there is an increasing demand for high color reproduction in color filters, which are made up of filter segments of each color.

[0004] In order to improve the color reproduction characteristics of a color filter, it is necessary to increase the content of the pigment in the photosensitive coloring composition or to increase the film thickness. However, in the method of increasing the content of the pigment, problems such as a decrease in sensitivity, deterioration in developability and resolution occur. In the method of increasing the film thickness, problems such as the exposure light not reaching the bottom of the film and the pattern shape becoming poor occur. In order to solve such problems, it is necessary to increase the sensitivity of the photosensitive coloring composition, and generally, (1) the addition of reactive double bonds to the resin, (2) the selection or increase of a photopolymerization initiator or sensitizer, (3) the selection or increase of a monomer, etc. are performed, and examples thereof include Patent Documents 1 and 2.

[0005] Furthermore, from the viewpoint of improving the image quality of color liquid crystal display devices and organic EL display devices, there is an increasing demand for improved color reproduction characteristics for color filters, such as the AdobeRGB standard, DCI standard, and BT2020 standard. Methods for responding to the demand for improved color reproduction characteristics include increasing the concentration of the colorant in the color filter or selecting a colorant with excellent coloring power. When the concentration of the colorant is increased, photolithography suitability is deteriorated, such as deterioration of pattern linearity and shape, so it is desirable to improve the coloring power of the colorant itself. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2001-264530 A [Patent Document 2] JP 2003-156842 A DISCLOSURE OF THEINVENTION [Problem to be solved by the invention]

[0007] The present invention aims to provide a photosensitive coloring composition that reduces the generation of foreign matter even in a coloring composition having a high colorant concentration, has an excellent pattern shape, and has a fast development speed, and a color filter and a liquid crystal display device using the same. [Means for solving the problem]

[0008] That is, the present invention provides a coloring composition comprising an organic pigment (A), a resin-type dispersant (B), and a binder resin (C), The organic pigment (A) contains one or more pigments selected from a zinc phthalocyanine pigment (A1) and an aluminum phthalocyanine pigment (A2), and The resin-type dispersant (B) comprises a basic resin-type dispersant (B1), and further comprises The present invention relates to a coloring composition, characterized in that the binder resin (C) contains a copolymer of a monomer (CL) having a homopolymer glass transition temperature of less than 0°C and a monomer (CH) having a homopolymer glass transition temperature of 150°C or higher, and the monomer (CL) accounts for 1 to 99 mass% and the monomer (CH) accounts for 1 to 50 mass% of the total monomers.

[0009] The present invention also relates to the above colored composition, wherein the binder resin (C) is a non-photosensitive alkali-soluble resin (C1) and / or a photosensitive alkali-soluble resin (C2).

[0010] The present invention also relates to the above colored composition, wherein the monomer (CL) having a homopolymer glass transition temperature of less than 0° C. is a compound represented by the following formula (1): Formula (1)

[0011] [ka]

[0012] (However, R 1 represents a hydrogen atom, and R 2 is a linear or branched alkyl group having 2 or more carbon atoms that does not have a ring structure, or R 1 represents a methyl group, and R 2 is a straight-chain or branched alkyl group having 5 or more carbon atoms that does not have a ring structure.

[0013] In the present invention, the binder resin (C) has a glass transition temperature calculated by the following formula (2): The coloring composition is characterized in that the temperature is 100° C. or lower. Equation (2) Fox equation 1 / Tg=W1 / Tg1+W2 / Tg2+···+W n / Tg n (However, from W1 to W n indicates the weight fraction of the n monomers used, and Tg1 to Tg n indicates the glass transition temperature (unit: absolute temperature "K") of a homopolymer (a single polymer of a monomer). In the case of a photosensitive alkali-soluble resin (C2), calculation is made for the monomer that constitutes the main chain. If there are multiple binder resins, calculate the glass transition temperature of each binder resin using formula (2), and then use formula (2) again to find the glass transition temperature of the entire binder resin. W1 to W n indicates the weight fraction of each binder resin, and Tg1 to Tg n indicates the glass transition temperature of each binder resin (unit is absolute temperature "K").

[0014] The present invention also relates to the above colored composition, wherein the binder resin (C) comprises a copolymer of a monomer (CL) having a homopolymer glass transition temperature of less than 0°C, a monomer (CM) having a homopolymer glass transition temperature of 0°C or more and less than 150°C, and a monomer (CH) having a homopolymer glass transition temperature of 150°C or more, and the monomer (CL) accounts for 1 to 99 mass%, the monomer (CM) for 1 to 80 mass%, and the monomer (CH) for 1 to 50 mass% of the total monomers.

[0015] The present invention also relates to the above colored composition, which contains 5 to 50 parts by mass of the basic resin-type dispersant (B1) based on 100 parts by mass of the binder resin (C).

[0016] The present invention also relates to the above colored composition, wherein the resin-type dispersant (B) contains an acidic resin-type dispersant (B2).

[0017] The present invention also relates to the above colored composition, wherein the organic pigment (A) contains a yellow pigment (a).

[0018] The present invention also relates to a photosensitive coloring composition comprising the above coloring composition, a polymerizable compound (D), and a photopolymerization initiator (E).

[0019] The present invention also relates to a color filter formed using the above-mentioned photosensitive coloring composition.

[0020] The present invention also relates to a liquid crystal display device comprising the above color filter. Effect of the Invention

[0021] According to the present invention, it is possible to provide a photosensitive coloring composition that reduces the generation of foreign matter even in a coloring composition having a high colorant concentration, has an excellent pattern shape, and has a fast development speed, and a color filter and a liquid crystal display device using the same. [Brief description of the drawings]

[0022] [Figure 1] FIG. 1 shows one form of a color file according to the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0023] Each of the components of the colored composition of the present invention will be described below. In this application, unless otherwise specified, the terms "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" respectively mean "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide". In addition, "CI" as used herein means Color Index (CI).

[0024] <Organic pigment (A)> The coloring composition of the present invention contains an organic pigment (A). The organic pigment (A) contains at least one selected from zinc phthalocyanine pigment (A1) and aluminum phthalocyanine pigment (A2), and preferably contains a halogen atom such as chlorine or bromine in the molecule. In addition, the coloring composition is preferably used in combination with a yellow pigment described below, and may be used in combination with other known organic pigments, inorganic pigments, dyes, etc. to achieve the required optical properties.

[0025] (Yellow pigment (a)) Yellow pigments include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 1 19, 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. are particularly preferable.

[0026] Inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine, iron blue, chromium oxide green, cobalt Examples of inorganic pigments include amber, red, and synthetic iron black. Inorganic pigments are used in combination with organic pigments to ensure good coatability, sensitivity, developability, and the like while maintaining a good balance between saturation and brightness.

[0027] <dye> As the dye, any of acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. may be used. In addition, the dye may be in the form of a derivative of these dyes or a lake pigment obtained by making the dye into a lake.

[0028] Furthermore, in the case of an acid dye having an acidic group such as sulfonic acid or carboxylic acid, or in the form of a direct dye, it is preferable to use a salt-forming compound obtained by salting using an inorganic salt of the acid dye, a salt-forming compound obtained by salting the acid dye with a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound, or a resin component having these functional groups, or to use the acid dye as a sulfonamide compound, which has excellent resistance, thereby making it possible to obtain a coloring composition having excellent fastness. Further, a salt-forming compound of an acid dye and a compound having an onium salt group is also preferred because it has excellent fastness, and more preferably, the compound having an onium salt group is a resin having a cationic group in the side chain.

[0029] In the case of a basic dye, it can be used after forming a salt with an organic acid, perchloric acid or a metal salt thereof. Among them, a salt-forming compound of a basic dye is preferred because of its excellent resistance and compatibility with pigments. In addition, a basic dye and a counter component acting as a counter ion, such as an organic sulfonic acid, an organic sulfuric acid, a fluorine-containing phosphorus anion compound, a fluorine-containing boron anion compound, etc., can be used. It is more preferable to use a salt-forming compound obtained by forming a salt with a nitrogen anion compound containing a cyano group, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye.

[0030] Furthermore, when the dye skeleton has a polymerizable unsaturated group, the dye can be made to have excellent durability, which is preferable.

[0031] Examples of the chemical structure of the dye include azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes, etc. Examples of the dye structure include dyes derived from dyes selected from the group consisting of oxonol-based dyes, merocyanine-based dyes, arylidene-based dyes, styryl-based dyes, cyanine-based dyes, squarylium-based dyes, and croconium-based dyes, quinophthalone-based dyes, phthalocyanine-based dyes, subphthalocyanine-based dyes, perinone-based dyes, indigo-based dyes, thioindigo-based dyes, quinoline-based dyes, nitro-based dyes, nitroso-based dyes, rhodamine-based dyes, and metal complex-based dyes thereof.

[0032] Among these dye structures, from the viewpoint of color properties such as hue, color separation, and color unevenness, dye structures derived from dyes selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and dye structures derived from dyes selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred. Specific dye compounds that can form the dye structure are described in "New Edition Dyes Handbook" (edited by the Society of Organic Synthesis Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), "Dyes Handbook" (edited by Okawara et al.; Kodansha, 1986), and the like.

[0033] <Minification of pigments> The pigment used in the coloring composition of the present invention is preferably finely divided before use. The method for finely dividing the pigment is not particularly limited, and any of wet grinding, dry grinding, and dissolution precipitation can be used. For example, the pigment can be finely divided by carrying out salt milling treatment using a kneader method, which is a type of wet grinding described below. The average primary particle size of the pigment determined by TEM (transmission electron microscope) is preferably in the range of 10 to 80 nm. If it is smaller than 10 nm, it becomes difficult to disperse it in an organic solvent, and if it is larger than 80 nm, a sufficient contrast ratio may not be obtained. For these reasons, the average primary particle size is more preferably in the range of 15 to 70 nm.

[0034] 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 with a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

[0035] Water-soluble inorganic salts include sodium chloride, barium chloride, potassium chloride, and sodium sulfate. From the viewpoints of both treatment efficiency and production efficiency, the water-soluble inorganic salt is preferably used in an amount of 50 to 2000 parts by mass, and most preferably 300 to 1000 parts by mass, per 100 parts by mass of the pigment.

[0036] The water-soluble organic solvent is not particularly limited as long as it functions to wet the pigment and the water-soluble inorganic salt, dissolves (mixes) in water, and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes easily evaporated, a high boiling point solvent with a boiling point of 120°C or more is preferable from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, and most preferably 50 to 500 parts by mass, relative to 100 parts by mass of the pigment.

[0037] When the pigment is subjected to salt milling, a resin may be added as necessary. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc. can be used. The resin used is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in the above organic solvents. The amount of the resin used is preferably in the range of 5 to 200 parts by mass relative to 100 parts by mass of the pigment.

[0038] <Resin-type dispersant (B)> <Basic resin type dispersant (B1)> The coloring composition of the present invention contains a resin type dispersant (B). It also contains a basic resin type dispersant (B1). The basic resin type dispersant (B1) is, for example, a copolymer obtained by radical polymerization of an ethylenically unsaturated monomer including an ethylenically unsaturated monomer having a basic group, and has a pigment affinity site including a basic group that adsorbs to the colorant and a site compatible with the colorant carrier, and functions to adsorb to the colorant and stabilize the dispersion in the colorant carrier.

[0039] Here, the basic group is a functional group having a nitrogen atom. Examples of the basic resin type dispersant (B1) include a nitrogen atom-containing graft copolymer, a nitrogen atom-containing acrylic block copolymer, a random copolymer, and a urethane resin type dispersant having a functional group including a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, or a nitrogen-containing heterocycle in a side chain.

[0040] In the present invention, the basic resin-type dispersant (B1) preferably has at least one structural unit selected from the group represented by the following general formulae (3), (4) and (5). [ka]

[0041] (In the general formula (3), R1 to R3 each independently represent a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, and two or more of R1 to R3 may be bonded to each other to form a cyclic structure. R4 represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y - indicates the counter anion.)

[0042] In the general formula (4), R5 and R6 are each independently a hydrogen atom or a group having a substituent. R5 and R6 may be bonded to each other to form a ring structure; R4 represents a hydrogen atom or a methyl group; and X represents a divalent linking group.

[0043] In the general formula (5), R7 is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or a cyclic group having 6 to 8 carbon atoms. 20 aryl groups, aralkyl groups having 7 to 12 carbon atoms, acyl groups, oxy radical groups, or OR 12 R 12 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group; R8, R9, and R 10and R 11 Each of R4 and R5 independently represents a methyl group, an ethyl group, or a phenyl group. R4 represents a hydrogen atom or a methyl group, and X represents a divalent linking group.

[0044] In general formula (3), R1 to R3 are more preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an aralkyl group having 7 to 16 carbon atoms which may have a substituent, and particularly preferably a methyl group, an ethyl group, a propyl group, a butyl group, or a benzyl group.

[0045] In the general formula (4), R5 and R6 are more preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, and a methyl group, an ethyl group, a propyl group, and a butyl group are particularly preferred.

[0046] In R7 of general formula (5), examples of the alkyl group having 1 to 18 carbon atoms include linear, branched, and cyclic alkyl groups, and specific examples thereof include a methyl group, an ethyl group, a normal propyl group, an isopropyl group, a n-butyl group, a t-butyl group, a n-hexyl group, a cyclohexyl group, a n-octyl group, and a hexadecyl group. Examples of the aryl group having 6 to 20 carbon atoms include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group. Examples of aralkyl groups having 7 to 12 carbon atoms include groups in which an alkyl group having 1 to 8 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms. Specific examples of such groups include a benzyl group, a phenethyl group, an α-methylbenzyl group, and a 2-phenylpropan-2-yl group. Examples of the acyl group include alkanoyl groups and aroyl groups having 2 to 8 carbon atoms, and specific examples thereof include an acetyl group and a benzoyl group. Among these, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an oxy radical group are particularly preferred, a hydrogen atom and a methyl group are more preferred, and a methyl group is most preferred.

[0047] In the general formulae (3), (4) and (5), examples of the divalent linking group X include a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, -CONH-R 13 -,-COO-R 14 -(However, R 13 and R 14 is a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an alkyloxyalkyl group having 2 to 10 carbon atoms), and preferably -CONH-R 13 -,-COO-R 1 4 In addition, in the above formula (3), Counteranion Y - As for Cl - , Br - , I - , ClO4 - , BF4 - , CH3COO - , PF6 - etc.

[0048] Specific examples of the ethylenically unsaturated monomer having a quaternary ammonium base, which is the precursor or partial structure of general formula (3), include alkyl (meth)acrylate-based quaternary ammonium salts such as (meth)acryloyloxyethyl trimethyl ammonium chloride, (meth)acryloyloxyethyl triethyl ammonium chloride, (meth)acryloyloxyethyl dimethyl benzyl ammonium chloride, and (meth)acryloyloxyethyl methyl morpholino ammonium chloride; alkyl (meth)acryloylamide-based quaternary ammonium salts such as (meth)acryloylaminopropyl trimethyl ammonium chloride, (meth)acryloylaminoethyl triethyl ammonium chloride, and (meth)acryloylaminoethyl dimethyl benzyl ammonium chloride; dimethyl diallyl ammonium methyl sulfate; and trimethyl vinyl phenyl ammonium chloride.

[0049] Specific examples of the ethylenically unsaturated monomer having a tertiary amine group, which is the precursor or partial structure of the general formula (4), include: N,N-Dimethylaminoethyl (meth)acrylate, N,N-Diethylaminoethyl (Meth)acrylates having a tertiary amino group, such as (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, and N,N-diethylaminopropyl (meth)acrylate; (meth)acrylamides having a tertiary amino group, such as N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl (meth)acrylamide; etc.

[0050] Specific examples of the ethylenically unsaturated monomer that serves as the precursor / partial structure of general formula (5) include compounds represented by the following general formulas (5-1) to (5-11).

[0051] [ka]

[0052] [ka]

[0053] In the general formulae (5-1) to (5-11), R4 represents a hydrogen atom or a methyl group.

[0054] Among these, 2,2,6,6-tetramethylpiperidyl methacrylate (a compound represented by the above general formula (5-1) in which R4 is a methyl group), 1,2,2,6,6-pentamethy Rupiperidyl methacrylate (a compound in which R4 in the above general formula (5-2) is a methyl group) Compounds) are preferred, and 1,2,2,6,6-pentamethylpiperidyl methacrylate is particularly preferred.

[0055] The structural units represented by general formulas (3), (4), and (5) may be contained alone or in combination of two or more kinds, and may be contained in any one of the forms of random copolymerization, block copolymerization, and graft copolymerization.

[0056] The structural units other than the structural units represented by the general formulae (3), (4), and (5) are not particularly limited as long as they are polymer structural units derived from monomers copolymerizable with the ethylenically unsaturated monomers that are precursors of the general formulae (3), (4), and (5), and can be appropriately selected depending on the application. The copolymerizable monomers are shown below.

[0057] For example, linear or branched alkyl (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth), tertiary butyl (meth)acrylate, isoamyl (meth)acrylate, octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate, isomyristyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate; cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, tertiary butyl cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate; (meth)acrylates having a heterocycle, such as tetrahydrofurfuryl (meth)acrylate and 3-methyl-3-oxetanyl (meth)acrylate; (Meth)acrylates having an aromatic ring, such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate, diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, triethylene glycol monoethyl ether (meth)acrylate, (poly)alkylene glycol monoalkyl ether (meth)acrylates such as ethyl ether (meth)acrylate, tripropylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, polypropylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monolauryl ether (meth)acrylate, polyethylene glycol monostearyl ether (meth)acrylate, and octoxypolyethylene glycol-polypropylene glycol (meth)acrylate; Phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhe xaethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethyl (meth)acrylate, paracumylphenoxyethylene glycol (meth)acrylate, paracumylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, and nonylphenoxypoly(ethylene glycol-propylene glycol) (meth)acrylate (Poly)alkylene glycol (meth)acrylates having an aromatic ring, such as those mentioned above; (Meth)acrylates having an alkyloxysilyl group, such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate; (meth)acryloxy-modified polydimethylsiloxanes (silicone macromers); Examples of the compound include N-substituted (meth)acrylamides such as (meth)acrylamide, dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; and nitriles such as (meth)acrylonitrile. Other examples include 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 vinyl fatty acid vinyls such as vinyl acetate and vinyl propionate.

[0058] Furthermore, a carboxyl group-containing ethylenically unsaturated monomer can also be used in combination. Examples of the silyl group-containing ethylenically unsaturated monomer include (meth)acrylic acid, (meth)acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2-(meth)acryloyloxyethyl phthalate, 2-(meth)acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth)acrylate, and ω-carboxypolycaprolactone (meth)acrylate.

[0059] Furthermore, structural units derived from ethylenically unsaturated monomers containing an amino group other than the structural units represented by general formulae (3), (4), and (5) may be used in combination, provided that the effects of the present invention are not impaired.

[0060] The molecular weight of the resin-type dispersant (B1) having a basic group of the present invention is preferably in the range of 1,000 or more and 100,000 or less, as calculated as polystyrene equivalent, on a weight average basis. When the weight average molecular weight is 1,000 or more, the dispersion stability is improved, and when it is 100,000 or less, the developability tends to be improved. The binder resin (C) preferably contains 5 to 50 parts by mass of the basic resin-type dispersant (B1) based on 100 parts by mass of the binder resin (C).

[0061] <Acidic resin type dispersant (B2)> In the coloring composition of the present invention, it is preferable to use an acidic resin type dispersant (B2) in addition to the basic resin type dispersant (B1). The acidic resin type dispersant (B2) is preferably the following resin (B2-1 to 2) having a dispersing ability and containing a carboxyl group (-COOH) in the molecule.

[0062] <Acidic resin type dispersant (B2-1)> The acidic resin-type dispersant (B2-1) comprises a polyester portion having a carboxyl group, which is obtained by reacting an acid anhydride group in one or more acid anhydrides selected from the group consisting of tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides with a hydroxyl group in a hydroxyl group-containing compound, and a vinyl polymer portion obtained by radical polymerization of an ethylenically unsaturated monomer; The resin type dispersant comprises: First, the polyester portion will be described. The polyester portion has a plurality of ester groups resulting from the reaction between an acid anhydride group and a hydroxyl group. [Tetracarboxylic acid anhydride] The tetracarboxylic dianhydride used in the present invention is 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2.2.Aliphatic tetracarboxylic dianhydrides such as 2-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, 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-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide 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 acid)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride.

[0063] The tetracarboxylic dianhydride used in the present invention is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. These may be used alone or in combination. Tetracarboxylic dianhydride is preferable as a component of the dispersant of the present invention from the viewpoint of pigment adsorption because it forms a dispersant having two carboxyl groups per tetracarboxylic dianhydride unit by reacting with a hydroxyl group-containing compound.

[0064] Moreover, from the viewpoint of adsorptivity to colorants, aromatic tetracarboxylic dianhydrides are preferably used in the present invention.

[0065] [Tricarboxylic acid anhydride] Examples of the tricarboxylic acid anhydride include aliphatic tricarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides.

[0066] Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid-1,2-anhydride, and 1,3,4-cyclopentanetricarboxylic acid anhydride.

[0067] Examples of aromatic tricarboxylic acids include benzenetricarboxylic anhydrides (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic anhydrides (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, etc.), 3,4,4'-benzophenonetricarboxylic anhydride, 3,4,4'-biphenylethertricarboxylic anhydride, 3,4,4'-biphenyltricarboxylic anhydride, 2,3,2'-biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, and 3,4,4'-biphenylsulfonetricarboxylic anhydride. Among the above, aromatic tricarboxylic anhydrides are preferably used in the present invention from the viewpoint of adsorption to pigments.

[0068] The molar ratio of acid anhydride groups in one or more acid anhydrides selected from tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides to hydroxyl groups in the hydroxyl group-containing compound is preferably acid anhydride groups / hydroxyl groups, from 0.5 to 1.5. If the ratio is less than 0.5 or more than 1.5, a large portion will not react, and the desired dispersant will not be obtained in many cases.

[0069] [Hydroxyl group-containing compound] The hydroxyl group-containing compound may have a hydroxyl group capable of reacting with an acid anhydride group, but is preferably a polyol such as a diol having a plurality of hydroxyl groups. In addition, a part or all of the polyol also serves as a bonding point with the vinyl polymer moiety. Examples of the polyol that is the bond origin with the vinyl polymer portion include at least one hydroxyl group-containing compound selected from the group consisting of compounds having two hydroxyl groups and one thiol group in the molecule and vinyl polymers containing a hydroxyl group at one end, etc. Examples include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin or 1-thioglycerol), 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.

[0070] The acidic resin type dispersant (B2-1) further includes an acidic resin type dispersant (B2-1-1) and an acidic resin type dispersant (B2-1-2) each having a characteristic vinyl polymer portion as shown below. <Acidic resin type dispersant (B2-1-1)> The vinyl polymer portion of the acidic resin-type dispersant (B2-1-1) is obtained by radical polymerization of 1) an ethylenically unsaturated monomer having at least one thermally crosslinkable functional group selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, and a blocked isocyanate group, 2) an ethylenically unsaturated monomer having a carboxyl group, and, if necessary, 3) other ethylenically unsaturated monomers.

[0071] 1-1) (Ethylenically unsaturated monomers having a hydroxyl group) The ethylenically unsaturated monomer having a hydroxyl group may be any monomer having a hydroxyl group and an ethylenically unsaturated double bond, and specifically, a (meth)acrylate monomer having a hydroxyl group, for example, a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4)-hydroxybutyl (meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate, and an alkyl-α-hydroxyalkyl acrylate such as ethyl-α-hydroxymethyl acrylate, or (meth)acrylamide monomers having a hydroxyl group, for example, N-(hydroxyalkyl)(meth)acrylamides such as N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, and N-(2-hydroxybutyl)(meth)acrylamide; Alternatively, a vinyl ether monomer having a hydroxyl group, for example, a hydroxyalkyl vinyl ether such as 2-hydroxyethyl vinyl ether, 2-(or 3-)hydroxypropyl vinyl ether, or 2-(or 3- or 4-)hydroxybutyl vinyl ether; Alternatively, there may be mentioned allyl ether monomers having a hydroxyl group, for example, hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, 2-(or 3-)hydroxypropyl allyl ether, and 2-(or 3- or 4-)hydroxybutyl allyl ether.

[0072] Furthermore, ethylenically unsaturated monomers obtained by adding alkylene oxides and / or lactones to the above-mentioned hydroxyalkyl (meth)acrylates, alkyl-α-hydroxyalkyl acrylates, N-(hydroxyalkyl) (meth)acrylamides, hydroxyalkyl vinyl ethers or hydroxyalkyl allyl ethers can also be used as ethylenically unsaturated monomers having a hydroxyl group in the method of the present invention. As the alkylene oxide to be added, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide, and combinations of two or more of these can be used. When two or more alkylene oxides are used in combination, the bonding form may be either random and / or block. As the lactone to be added, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, or a combination of two or more of these may be used. Both an alkylene oxide and a lactone may be added.

[0073] 1-2) (Ethylenically unsaturated monomers having an oxetane group) Examples of ethylenically unsaturated monomers having an oxetane group include (vinyloxyalkyl) alkyloxetane, (meth)acryloyloxyalkyloxetane, and [(meth)acryloyloxyalkyl] alkyloxetane. Among these, (3-ethyloxetan-3-yl)methyl methacrylate is preferred. Examples of commercially available products include ETERNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate) (manufactured by Ube Industries).

[0074] 1-3) (ethylenically unsaturated monomer having a t-butyl group) Examples of the ethylenically unsaturated monomer having a t-butyl group include t-butyl methacrylate and t-butyl acrylate.

[0075] 1-4) (Ethylenically unsaturated monomers having blocked isocyanate groups) Examples of ethylenically unsaturated monomers having a blocked isocyanate group include 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate, 2-[(3, 5-Dimethylpyrazolyl)carbonylamino]ethyl methacrylate and the like. Commercially available products include Karenz MOI-BM (2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate) (manufactured by Showa Denko), Karenz MOI -BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate) (manufactured by Showa Denko).

[0076] The content of the ethylenically unsaturated monomer having an oxetane group, the ethylenically unsaturated monomer having a t-butyl group, and the ethylenically unsaturated monomer having a blocked isocyanate group is preferably 5 to 90% by mass, and particularly preferably 20 to 60% by mass, based on the total amount of the ethylenically unsaturated monomers. If it is 5% by mass or more, it is possible to obtain a colored composition having excellent resistance due to the effect of crosslinking, and if it is 90% by mass or less, it is preferable because the stability of the composition is good.

[0077] 2) (Ethylenically unsaturated monomers having a carboxyl group) Examples of the ethylenically unsaturated monomer having a carboxyl group include (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc. Among these, (meth)acrylic acid is preferred from the viewpoints of copolymerization reactivity and easy availability.

[0078] 3) [Other ethylenically unsaturated monomers] In the vinyl polymer portion of the dispersant of the present invention, ethylenically unsaturated monomers other than the ethylenically unsaturated monomer having a thermally crosslinkable functional group and the ethylenically unsaturated monomer having a carboxyl group may be radically polymerized. Examples of other ethylenically unsaturated monomers include, in addition to the above-mentioned ethylenically unsaturated monomers, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate, and the like. Alkyl (meth)acrylates such as acrylate; Aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate; Heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate; alkoxypolyalkylene glycol (meth)acrylates such as methoxypolypropylene glycol (meth)acrylate and ethoxypolyethylene glycol (meth)acrylate; N-substituted (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, and acryloylmorpholine; Amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate; and nitriles such as (meth)acrylonitrile. In this specification, (meth)acrylate refers to methacrylate or acrylate, and (meth)acrylamide refers to methacrylamide or acrylamide.

[0079] Further, examples of monomers that can be used in combination with the above acrylic monomers include 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.

[0080] <Acidic resin type dispersant (B2-1-2)> The vinyl polymer portion of the acidic resin-type dispersant (B2-1-2) is a polymer obtained by radically polymerizing an ethylenically unsaturated monomer and modifying it so as to have a (meth)acryloyl group. Specifically, the method for producing the acidic resin-type dispersant (B2-1-2) is to react a compound having a (meth)acryloyl group and a functional group with a polymer obtained by polymerizing a monomer containing an ethylenically unsaturated monomer having a functional group that reacts with the functional group. For example, the combination of glycidyl methacrylate with a polymer having a hydroxyl group or a carboxyl group, the combination of methacryloyloxyethyl isocyanate with a polymer having a hydroxyl group or a carboxyl group, etc. can be mentioned. A polymer having a hydroxyl group or a carboxyl group can also be obtained by subjecting a polymer having a glycidyl group or an acid anhydride group to a ring-opening reaction. For example, the dispersants described in JP-A-2011-157416 can be mentioned.

[0081] <Acidic resin type dispersant (B2-2)> The acidic resin-type dispersant (B2-2) is a dispersant represented by the following general formula (6), and specifically, is a dispersant described in JP-A-2007-140487. General formula (6) (HOOC-) m -R 1 -(-COO-[-R 3 -COO-] n -R 2 ) t (In the formula, R 1 is a tetravalent tetracarboxylic acid compound residue, R 2is a monoalcohol residue, R 3 Is Ra m is 2 or 3, n is an integer from 1 to 50, and t is (4-m).

[0082] <Commercially available resin-type dispersants> In the coloring composition of the present invention, commercially available known resin type dispersants may be used as the basic resin type dispersant (b1), phosphoric acid type resin type dispersant (b2), or carboxylic acid type resin type dispersant (b4), or may be used in combination as appropriate. Commercially available resin type dispersants include Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, and 215 manufactured by BYK-Chemie Japan. 5, 2163, 2164 or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, LPN6919, BYK-LPN21116, BYK-LPN21324, or Lactimon, Lactimon-WS or Bykumen, SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20 000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 40 80, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0083] <Dye derivative (b)> The coloring composition used in the present invention may contain a dye derivative (b) as required. As the dye derivative used in the present invention, known dye derivatives having an acidic group, a basic group, a neutral group, etc. in the organic dye residue can be used. For example, compounds having an acidic substituent such as a sulfo group, a carboxy group, a phosphoric acid group, etc., 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 organic pigments 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.

[0084] Specifically, diketopyrrolopyrrole dye derivatives are described in JP 2001-220520 A, WO2009 / 081930 B, WO2011 / 052617 B, WO2012 / 102399 B, and JP 2017-156397 A. Phthalocyanine dye derivatives are described in JP 2007-226161 A, WO2016 / 163351 B, JP 2017-165820 B, and JP 5753266 A. Anthraquinone dye derivatives are described in JP 2007-226161 A, WO2016 / 163351 B, JP 2017-165820 B, and JP 5753266 A. JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009 / 025325 pamphlet; quinacridone dye derivatives include JP-A-48-54128, JP-A-03-9961, and JP-A-2000-273383; dioxazine dye derivatives include JP-A-2011-162662; thiazine indigo dye derivatives include JP-A-2007-314785 As triazine-based dye derivatives, JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681, as benzoisoindole-based dye derivatives, JP-A-2009-57478, as quinophthalone-based dye derivatives, JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-2 Examples of naphthol-based dye derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439; examples of azo-based dye derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092; examples of acidic substituents include those described in JP-A-2004-307854; and examples of basic substituents include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404, and the like.In these documents, the dye derivative is sometimes described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the compound having a substituent such as an acidic group, a basic group, or a neutral group in the organic dye residue is synonymous with the dye derivative.

[0085] <Binder resin (C)> The coloring composition of the present invention contains a binder resin (C). The binder resin (C) contains a copolymer of a monomer (CL) having a homopolymer glass transition temperature of less than 0° C. and a monomer (CH) having a homopolymer glass transition temperature of 150° C. or higher. The polymerization ratio of the monomer (CL) to the monomer (CH) is 1 to 99 mass % of the monomer (CL) and 1 to 50 mass % of the monomer (CH) in 100 mass % of all monomers that are precursors of the copolymer.

[0086] <Monomer (CL)> The monomer (CL) having a homopolymer glass transition temperature of less than 0° C. is represented by the following formula (1). Formula (1)

[0087] [ka]

[0088] (However, R 1 represents a hydrogen atom, and R 2 is a linear or branched alkyl group having 2 or more carbon atoms that does not have a ring structure, or R 1 represents a methyl group, and R 2 is a straight-chain or branched alkyl group having 5 or more carbon atoms that does not have a ring structure. Monomer As specific examples of (CL), the abbreviation and the glass transition temperature of the homopolymer are shown below. n -Butyl acrylate (n-BA: -55℃) Isoamyl acrylate (IAA: -45℃) 2-Ethylhexyl acrylate (2-EHA: -70℃) LaUryl methacrylate (LMA: -65℃) Stearyl methacrylate (SMA: -100℃)

[0089] <Monomer (CH)> As specific examples of monomers (CH), the abbreviations and the glass transition temperatures of the homopolymers are shown below. Dicyclopentanyl methacrylate (DCPMA: 175℃) Isobornyl methacrylate (IBMA: 180℃) Adamantyl acrylate (ADA: 153℃) Adamantyl methacrylate (ADMA: 250℃)

[0090] In addition, the binder resin (C) preferably contains a copolymer of a monomer (CL) having a homopolymer glass transition temperature of less than 0°C, a monomer (CM) having a homopolymer glass transition temperature of 0°C or more and less than 150°C, and a monomer (CH) having a homopolymer glass transition temperature of 150°C or more. The polymerization ratio of the monomer (CL), the monomer (CM) and the monomer (CH) is 1 to 99 mass% for the monomer (CL), 1 to 80 mass% for the monomer (CM), and 1 to 50 mass% for the monomer (CH) in 100 mass% of all monomers which are precursors of the copolymer.

[0091] <Monomer (CM)> As specific examples of monomers (CM), the abbreviations and the glass transition temperatures of the homopolymers are listed below. Acrylic acid (AA: 106°C) Glycidyl methacrylate (GMA: 46℃) Styrene (St:80℃) Ethyl methacrylate (EMA: 65℃) Methyl methacrylate (MMA: 105℃) Benzyl methacrylate (BzMA: 54℃) Hydroxyethyl methacrylate (HEMA: 55℃) n-Butyl methacrylate (n-BMA: 20℃) i-Butyl methacrylate (i-BMA: 48℃) t-Butyl methacrylate (t-BMA: 107℃)

[0092] Furthermore, the binder resin (C) more preferably has a glass transition temperature calculated from the following formula (2) of 100° C. or lower. Equation (2) Fox equation 1 / Tg=W1 / Tg1+W2 / Tg2+···+W n / Tg n (However, from W1 to W n indicates the weight fraction of the n monomers used, and Tg1 to Tg n indicates the glass transition temperature (unit: absolute temperature "K") of a homopolymer (a single polymer of a monomer). In the case of a photosensitive alkali-soluble resin (C2), calculation is made for the monomer that constitutes the main chain. Here, the monomer that constitutes the main chain is the monomer used when polymerizing the resin before it is modified to impart photosensitivity. The glass transition temperature of a resin is greatly affected by the structure near the main chain, but since the structure near the main chain itself does not change before and after modification to impart photosensitivity, it is calculated for the monomer that constitutes the main chain. Note that when there are multiple binder resins, in formula (2), the glass transition temperature of each binder resin is calculated using formula (2), and then the glass transition temperature of the entire binder resin is calculated using formula (2). When calculating again, W1 to W n indicates the weight fraction of each binder resin, and Tg1 to Tg n indicates the glass transition temperature of each binder resin (unit is absolute temperature "K").

[0093] The binder resin (C) is preferably a resin having a transmittance of 80% or more, more preferably 95% or more, in the entire wavelength range of 400 to 700 nm. As the binder resin, a thermoplastic resin, an active energy ray curable resin having an ethylenically unsaturated double bond, etc., can be used, and further, from the viewpoint of developability, an alkali-soluble resin is preferable. The resin may contain a thermoplastic resin that is not curable by active energy rays, and this resin is also preferably alkali-soluble. These may be used alone or in combination of two or more kinds.

[0094] The content of the binder resin in the coloring composition of the present invention is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on the total mass of the colorant (100 parts by mass). It is preferably used in an amount of 20 parts by mass or more because of good film-forming properties and various resistances, and it is preferably used in an amount of 400 parts by mass or less because of a high colorant concentration and good color characteristics.

[0095] <Thermoplastic resin> Examples of thermoplastic resins that can be used as binder 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. <Alkali-soluble resin> The thermoplastic resin is preferably alkali-soluble, and examples thereof include resins having acidic groups such as carboxyl groups and sulfonic groups. Specific examples of the resin include acrylic resins having acidic groups, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers. Among these, at least one resin selected from acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers, particularly those having acidic groups and / or An alkali-soluble resin having a hydroxyl group is preferably used because of its high developability, heat resistance and transparency.

[0096] The alkali-soluble resin is intended to impart development solubility in the alkali development step during the production of a color filter, and has an acid group and / or a hydroxyl group.

[0097] <Photosensitive alkali-soluble resin (C2)> The binder resin (C) is a non-photosensitive alkali-soluble resin (C1) and / or a photosensitive alkali-soluble resin (C2). The binder resin (C) used in the present invention preferably has an ethylenically unsaturated double bond in order to further improve the photosensitivity. In particular, by using a resin into which an ethylenically unsaturated double bond has been introduced by the following method (i) or (ii), the resin is three-dimensionally crosslinked when exposed to active energy rays to form a coating film, thereby increasing the crosslink density and improving chemical resistance.

[0098] [Method (i)] An example of the method (i) is a method in which an ethylenically unsaturated double bond and a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond are added to the side-chain epoxy group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having an epoxy group with one or more other monomers, and the hydroxyl group thus generated is reacted with a polybasic acid anhydride to introduce an ethylenically unsaturated double bond and a carboxyl group.

[0099] Examples of the ethylenically unsaturated monomer having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. These may be used alone or in combination of two or more. From the viewpoint of reactivity with the unsaturated monobasic acid in the next step, glycidyl (meth)acrylate is preferred. p) Acrylate is preferred.

[0100] Examples of the unsaturated monobasic acid include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position. These may be used alone or in combination of two or more kinds.

[0101] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc., which may be used alone or in combination of two or more. If necessary, for example, to increase the number of carboxyl groups, a tricarboxylic acid anhydride such as trimellitic anhydride or a tetracarboxylic acid dianhydride such as pyromellitic dianhydride may be used to hydrolyze the remaining anhydride groups. In addition, if tetrahydrophthalic anhydride or maleic anhydride having an ethylenically unsaturated double bond is used as the polybasic acid anhydride, the number of ethylenically unsaturated double bonds can be further increased.

[0102] As a method similar to the method (i), for example, there is a method in which an ethylenically unsaturated monomer having an epoxy group is added to a part of the side chain carboxyl groups of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a carboxyl group with one or more other monomers, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

[0103] [Method (ii)] Method (ii) includes a method in which an ethylenically unsaturated monomer having a hydroxyl group is used and copolymerized with another monomer of an unsaturated monobasic acid having a carboxyl group or with another monomer, and the side chain hydroxyl group of the copolymer is reacted with an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group.

[0104] Examples of ethylenically unsaturated monomers having a hydroxyl group 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, or cyclohexanedimethanol mono(meth)acrylate, which may be used alone or in combination of two or more. In addition, polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above-mentioned hydroxyalkyl (meth)acrylates, and polyester mono(meth)acrylates obtained by addition of poly(γ-valerolactone), poly(ε-caprolactone, and / or poly(12-hydroxystearic acid) may also be used. From the viewpoint of suppressing foreign matter in the coating, 2-hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred, and from the viewpoint of sensitivity, it is preferred to use a compound having 2 to 6 hydroxyl groups, with glycerol mono(meth)acrylate being even more preferred.

[0105] Examples of the ethylenically unsaturated monomer having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate, but are not limited to these, and two or more of them can be used in combination.

[0106] Examples of monomers constituting the alkali-soluble resin include the following: 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, ) acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate; Alternatively, examples of the monomer include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

[0107] Alternatively, 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 N-substituted maleimides such as N-(4-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine. Examples of the polyimides include imides, 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.

[0108] Also usable are carboxyl group-containing ethylenically unsaturated monomers, such as acrylic acid, methacrylic acid, ε-caprolactone-added acrylic acid, ε-caprolactone-added methacrylic acid, itaconic acid, maleic acid, fumaric acid, and crotonic acid.

[0109] Hydroxyl-containing ethylenically unsaturated monomers can also be used. Examples of hydroxyl-containing ethylenically unsaturated monomers include 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxypropyl (meth)acrylate, and the like. Examples of the hydroxyalkyl (meth)acrylates include hydroxybutyl (meth)acrylate and cyclohexane dimethanol mono(meth)acrylate. Examples of the hydroxyalkyl (meth)acrylate include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the hydroxyalkyl (meth)acrylates, and (poly)ester mono(meth)acrylates obtained by addition of (poly)γ-valerolactone, (poly)ε-caprolactone, and / or (poly)12-hydroxystearic acid.

[0110] Also, ethylenically unsaturated monomers containing a phosphate ester group can be used. Examples of the ester group-containing ethylenically unsaturated monomer include monomers that can be obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer with a phosphorylating agent such as phosphorus pentoxide or polyphosphoric acid.

[0111] <Non-photosensitive alkali-soluble resin (C1)> The binder resin (C) used in the present invention can contain a non-photosensitive alkali-soluble resin (C1) that does not have an ethylenically unsaturated double bond in order to adjust the degree of hardening of the coating film. By synthesizing the resin using at least one carboxyl group-containing ethylenically unsaturated monomer and one or more of the other ethylenically unsaturated monomers, and not providing an ethylenically unsaturated bond to the side chain, an alkali-soluble resin that does not have an ethylenically unsaturated double bond can be obtained.

[0112] The alkali-soluble resin in the present invention is preferably a resin having a spectral transmittance of preferably 80% or more, more preferably 95% or more, over the entire wavelength range of 400 to 700 nm in the visible light region.

[0113] The weight average molecular weight (Mw) of the alkali-soluble resin in the present invention is 2,000 to 40,000, preferably 3,000 to 300,000, more preferably 4,000 to 20,000, in order to impart alkali development solubility. The value of Mw / Mn is preferably 10 or less. If the weight average molecular weight (Mw) is less than 2,000, the adhesion to the substrate decreases, making it difficult to leave an exposed pattern. If it exceeds 40,000, the alkali development solubility decreases, residues are generated, and the linearity of the pattern deteriorates. The acid value of the alkali-soluble resin in the present invention is from 50 to 200 (KOH mg / g) in order to impart solubility in alkali development, and is preferably in the range of from 70 to 180. More preferably, it is in the range of 90 to 170. If the acid value is less than 50, the solubility in alkaline development decreases, residues are generated, and linearity of the pattern deteriorates. If it exceeds 200, adhesion to the substrate decreases, making it difficult to leave an exposed pattern.

[0114] <Thermosetting compound (CE)> In the present invention, a thermosetting compound (CE) can be further contained in combination with the binder resin (C). When a color filter is produced using the coloring composition for color filters of the present invention, the thermosetting compound reacts during firing of the filter segments to increase the crosslink density of the coating film, thereby improving the heat resistance of the filter segments, suppressing pigment aggregation during firing of the filter segments, and improving the contrast ratio.

[0115] The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds, but the present invention is not limited thereto. In the coloring composition for color filters of the present invention, epoxy compounds and oxetane compounds are preferably used.

[0116] (Epoxy compound (CE-1)) The epoxy compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of such epoxy compounds include bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, etc.). Polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, Examples of epoxy resins include polycondensates of phenols and aromatic dichloromethyls (α,α,α',α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins, but are not limited to these as long as they are commonly used epoxy compounds. These may be used alone or in combination of two or more.

[0117] Examples of commercially available products include Epicoat 807, Epicoat 815, Epicoat 825, Epicoat 827, Epicoat 828, Epicoat 190P, Epicoat 191P (all trade names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicoat 1004, Epicoat 1256 (all trade names; manufactured by Japan Epoxy Resins Co., Ltd.), TECHMORE VG3101L (trade name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (trade names; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), JER157S65, 157S70 (trade name; manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201 (trade name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (all trade names; manufactured by Japan Epoxy Resin Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (all trade names; manufactured by Nippon Kayaku Co., Ltd.), Examples of such compounds include Celloxide 2021, EHPE-3150 (all trade names; manufactured by Daicel Chemical Industries, Ltd.), Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 (all trade names; manufactured by Nagase ChemteX Corporation), TEPIC-L, TEPIC-H, and TEPIC-S (manufactured by Nissan Chemical Industries, Ltd.). These include, but are not limited to, the following:

[0118] The amount of the epoxy compound is preferably 0.5 to 300 parts by mass, and more preferably 1.0 to 50 parts by mass, relative to 100 parts by mass of the colorant. If the amount is less than 0.5 parts by mass, the effect of improving the contrast ratio and heat resistance is small, and if the amount is more than 300 parts by mass, problems may occur when forming filter segments by photolithography.

[0119] (Oxetane Compound (CE-2)) It is preferable to add an oxetane compound to the photosensitive coloring composition of the present invention. As the oxetane compound, a known compound having an oxetane group can be used without any particular limitation. The oxetane compound includes those in which the oxetane group is monofunctional, those in which the oxetane group is bifunctional, and those in which the oxetane group is bifunctional or more.

[0120] Examples of compounds having one functional oxetane group include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, and 3-ethyl-3 3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane, and the like. Specific examples include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Ltd., and OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd.

[0121] Examples of compounds having two functional oxetane groups include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, and di[1-ethyl(3-oxetanyl)]methyl ether-3-ethyl-3-hydroxymethyloxetane. 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycose bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl -3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F(3-ethyl-3-oxetanylmethyl) ether, and the like. Specific examples include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

[0122] Examples of the oxetane group having two or more functional groups include Pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa Examples of the polymers include (3-ethyl-3-oxetanylmethyl)ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl)ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl)ether, resins containing oxetane groups (e.g., oxetane-modified phenol novolac resins described in Japanese Patent No. 3783462, etc.), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the above-mentioned OXE-30. Such polymers can be obtained by using known polymerization methods.

[0123] The content of the oxetane compound used in the coloring composition of the present invention is usually 0.5 to 50 mass%, preferably 1 to 40 mass%, based on 100 mass% of the solid content of the coloring composition. When the content of the oxetane compound is within the above range, it is preferable because an excellent coating film having good water stain resistance and high chemical resistance can be obtained.

[0124] (Melamine compounds) The melamine compound in the present invention refers to a compound having a melamine ring structure. The melamine compound may be a low molecular weight compound or a high molecular weight compound such as a resin. In the present invention, the melamine compound is preferably a methylol type or an ether type, and the methylol per melamine ring is preferably 1 to 100%. A melamine compound having an average of 5.0 or more methylol groups and / or ether groups. If the average number of methylol groups and / or ether groups per melamine ring is less than 5.0, there are few reaction sites and the crosslinked structure during curing is not sufficiently dense, which may reduce the effects of suppressing the decrease in contrast ratio due to the heat treatment process and improving NMP resistance.

[0125] Examples of commercially available products include, but are not limited to, Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 (manufactured by Sanwa Chemical Co., Ltd.), and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 (manufactured by Nippon Cytec Industries Co., Ltd.).

[0126] Among these, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.), Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Nippon Cytec Industries Co., Ltd.), and the like, which have an average of 5.0 or more methylol groups and / or ether groups per melamine ring, are preferred in that they can provide a dense crosslinked structure.

[0127] (hardening agent) In addition, the coloring composition for color filters of the present invention may contain a curing agent (curing accelerator) or the like as necessary to assist the curing of the thermosetting compound. As the curing agent, amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, and the like are effective, but are not particularly limited thereto, and any curing agent may be used as long as it can react with the thermosetting compound. As the curing agent, for example, amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2 -phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine·isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine·isocyanuric acid adduct, etc.) can be used. These may be used alone or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the thermosetting compound.

[0128] <Polymerizable compound (D)> The photosensitive coloring composition of the present invention includes a photosensitive coloring composition characterized by comprising a coloring composition, a polymerizable compound (D), and a photopolymerization initiator (E). The polymerizable compound (D) includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to produce a transparent resin.

[0129] Examples of monomers and oligomers that are cured by exposure to ultraviolet light or heat to produce a transparent resin include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and ethyl (meth)acrylate. (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, trimethylolpropane EO modified tri(meth)acrylate, isocyanuric acid EO modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanedi Examples of the acrylic acid esters and methacrylic acid esters include all 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 methylol melamine, epoxy (meth)acrylate, and urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, and acrylonitrile, but are not necessarily limited thereto.

[0130] Commercially available products of these include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, M-310, and M-32 manufactured by Toagosei Co., Ltd. Suitable examples of the polymerizable compound that can be used include, for example, M-1, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, and M-101A, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, and #405 manufactured by Osaka Organic Chemical Co., Ltd., and NK Ester A-9300 manufactured by Shin-Nakamura Chemical Co., Ltd.

[0131] (Polymerizable compound having an acid group) The photopolymerizable monomer in the present invention may contain a photopolymerizable monomer having an acid group, such as a sulfonic acid group, a carboxyl group, or a phosphoric acid group.

[0132] Examples of photopolymerizable monomers having an acid group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates; and the like. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates, such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, with dicarboxylic acids, such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and free carboxyl group-containing monoesters 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 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl ... Examples of the free carboxyl group-containing oligoesters of monohydroxymonoacrylates such as hydroxypropyl methacrylate or monohydroxymonomethacrylates are mentioned, but the effects of the present invention are not limited to these.

[0133] As commercially available products thereof, Viscoat #2500P manufactured by Osaka Organic Coatings Co., Ltd., and Aronix M-5300, M-5400, M-5700, M-510, M-520 manufactured by Toagosei Co., Ltd., and the like can be suitably used.

[0134] (Polymerizable compound having urethane bond) The photopolymerizable monomer in the present invention may contain a photopolymerizable monomer containing at least one ethylenically unsaturated bond and at least one urethane bond. For example, there may be mentioned a multifunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a multifunctional isocyanate, or a multifunctional urethane acrylate obtained by reacting an alcohol with a multifunctional isocyanate and further reacting the alcohol with a (meth)acrylate having a hydroxyl group.

[0135] Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol propylene oxide modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0136] Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

[0137] As commercially available products thereof, AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, DAUA-167 manufactured by Kyoeisha Chemical Co., Ltd., UA-160TM manufactured by Shin-Nakamura Chemical Co., Ltd., UV-4108F, UV-4117F manufactured by Osaka Organic Chemical Industry Co., Ltd., and the like can be suitably used. The above photopolymerizable monomers can be used alone or in combination of two or more kinds in any ratio as required.

[0138] The amount of the photopolymerizable monomer is preferably 1 to 50 parts by mass based on the total solid content of the photosensitive coloring composition (100 parts by mass), and more preferably 2 to 40 parts by mass from the viewpoints of photocurability and developability.

[0139] <Photopolymerization initiator (E)> The photosensitive coloring composition of the present invention contains a photopolymerization initiator (E). By containing the photopolymerization initiator (E), the composition can be cured by ultraviolet irradiation and a filter segment can be formed by a photolithography method. It is preferable to add the photopolymerization initiator (E) to prepare a solvent-developable or alkali-developable photosensitive coloring composition.

[0140] The photopolymerization initiator (E) may be 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropyl phenone), acetophenone compounds such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzoin, Benzoin compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanes thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone, and other thioxanthone-based 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(trichloromethyl)-s-triazine, 2- triazine compounds such as 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 oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds. These photopolymerization initiators can be used alone or in combination of two or more kinds in any ratio as required.

[0141] Commercially available products include acetophenone compounds, all manufactured by IGM Resins, such as "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one), "Omnirad 369E" (2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone), and "Omnirad 379EG" (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), and phosphine compounds, all manufactured by IGM Resins, such as "Omnirad 819" (bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide) and "Omnirad TPO" (diphenyl-2,4,6-trimethylbenzoylphosphine oxide).

[0142] In the present invention, among these, it is preferable to contain an oxime ester compound.

[0143] (Oxime ester compounds) In oxime ester compounds, the NO bond of the oxime is cleaved by absorbing ultraviolet light, generating iminyl radicals and alkyloxy radicals. Since it further decomposes to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may decrease, and the degree of hardening of the coating film may decrease, but oxime ester compounds are preferably used because they have high quantum efficiency.

[0144] Commercially available products of these oxime ester compounds include 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (IR GACURE OXE-01), Ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (IRGACURE OXE 02), N-1919 (ADEKA), TRONLYTR-P TRONLY TR-PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309 (all manufactured by Changzhou Strong New Materials Co., Ltd.) and the like are commercially available. In addition, oxime ester photopolymerization initiators described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, and the like can also be used.

[0145] The content of the oxime ester compound is preferably 2 to 50 parts by mass, and more preferably 2 to 30 parts by mass, based on 100 parts by mass of the colorant, from the viewpoint of photocurability and developability. If it is less than 2 parts by mass, the adhesion of the formed pattern to the substrate is deteriorated, and if it exceeds 50 parts by mass, problems with developability may occur, and a decrease in brightness after heat treatment at 230°C may occur.

[0146] <Sensitizer (H)> Furthermore, the photosensitive coloring composition of the present invention may contain a sensitizer. Examples of sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzil and camphorquinone, polymethine dyes such as 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, tetraquinoxaliroporphyrazine 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, acyl oxides, methylphenyl glyoxylate, 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.

[0147] Among the above sensitizers, particularly suitable sensitizers include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole are used.

[0148] These sensitizers may be used alone or in combination of two or more kinds in any ratio as required. Commercially available products include "KAYACURE DETX-S" (2,4-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) and "CHEMARK DEABP" (4,4'-bis(diethylamino)benzophenone, manufactured by Chemark Chemical Co., Ltd.).

[0149] More specifically, examples of the sensitizers include, but are not limited to, those described in "Dye Handbook" edited by Makoto Okawara et al. (Kodansha, 1986), "Chemistry of Functional Dyes" edited by Makoto Okawara et al. (CMC, 1981), "Tokushu No Futoshi Zairyo" edited by Chuzaburo Ikemori et al., and "Tokushu No Futoshi Zairyo" (CMC, 1986). In addition, a sensitizer that absorbs light from the ultraviolet to near infrared region may also be contained.

[0150] The content of the sensitizer when used is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, relative to 100 parts by mass of the photoradical polymerization initiator contained in the coloring composition, from the viewpoints of photocurability and developability.

[0151] <Thiol-based chain transfer agents (I)> The photosensitive coloring composition of the present invention preferably contains a thiol-based chain transfer agent as a chain transfer agent. By using thiol together with a photopolymerization initiator, the thiol acts as a chain transfer agent in the radical polymerization process after light irradiation, and generates a thiyl radical that is not easily inhibited by oxygen, so that the obtained coloring composition has high sensitivity.

[0152] Also preferred is a polyfunctional aliphatic thiol having two or more thiol groups bonded to an aliphatic group such as a methylene or ethylene group. More preferred is a polyfunctional aliphatic thiol having four or more thiol groups. By increasing the number of functional groups, the polymerization initiation function is improved, and curing can be achieved from the surface of the pattern to the vicinity of the substrate.

[0153] 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, ... Examples of the thiopropionate include taerythritol 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.

[0154] These thiol chain transfer agents can be used alone or in combination of two or more.

[0155] The content of the thiol chain transfer agent is preferably 1.0 to 10% by mass, more preferably 2.0 to 8.0% by mass, based on the total solid content of the colored composition. Within this range, the effect of the chain transfer agent is increased, and the sensitivity, taper shape, wrinkles, film shrinkage rate, etc. are improved.

[0156] <Polymerization inhibitor (J)> The photosensitive coloring composition of the present invention may contain a polymerization inhibitor in order to prevent photosensitivity due to diffracted light from a mask during exposure. By adding a polymerization inhibitor, it is possible to obtain an effect of preventing curing from progressing beyond the desired pattern due to chain polymerization caused by exposure to light.

[0157] 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-t-butyl catechol, 3-t-butyl catechol, 4-t-butyl catechol, and 3,5-di-t-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, and 2-n-butyl Examples of the polymerization inhibitor include alkyl resorcinol compounds such as ruresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol, alkyl hydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, and 2,5-di-t-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 phloroglucin. The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass relative to 100 parts by mass of the coloring composition excluding the solvent. In this range, the effect of the polymerization inhibitor becomes large, and the linearity of the taper, wrinkles of the coating film, pattern resolution, and the like become good.

[0158] <Ultraviolet absorber (K)> The photosensitive coloring composition of the present invention may contain an ultraviolet absorber. The ultraviolet absorber in the present invention is an organic compound having an ultraviolet absorbing function, and examples of the ultraviolet absorber include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

[0159] The content of the ultraviolet absorber is preferably 5 to 70% by mass, based on 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. If the content of the ultraviolet absorber is less than the above, the effect of the ultraviolet absorber is small and the resolution cannot be ensured, whereas if the content is more than the above, the sensitivity is reduced, and problems such as pixel peeling and hole diameter becoming larger than the designed value may occur.

[0160] In this case, when the photosensitive coloring composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

[0161] The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass in 100% by mass of the solid content of the photosensitive coloring composition. If the total content of the photopolymerization initiator and the ultraviolet absorber is less than the above, adhesion may be weakened and pixel peeling may occur, and if it is more than the above, the sensitivity may be too high and the resolution may be poor.

[0162] In this case, when the photosensitive coloring composition contains a sensitizer, the content of the sensitizer is included in the content of the photopolymerization initiator.

[0163] Benzotriazole organic compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, Triazole, 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-octyl phenyl)- 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, reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-t-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-t-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate. In addition, oligomer-type and polymer-type compounds having a benzotriazole structure can also be used.

[0164] More specifically, TINUVIN P, PS, 234, and 326 manufactured by BASF Corporation are , 329, 384-2, 900, 928, 99-2, 1130, ADK STAB LA-29, LA-31RG, LA-32, LA-36 manufactured by ADEKA CORPORATION, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Chemical Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

[0165] As triazine-based organic compounds, 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 of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of the product 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. Other oligomer and polymer type compounds having a triazine structure can also be used.

[0166] More specifically, KEMISORB 102 manufactured by Chemipro Chemicals and TIN UVIN 400, 405, 460, 477, 479, 1577ED, ADEKA Kastab LA-46, LA-F70, Sun Chemical CYASORB UV-1164 etc.

[0167] Benzophenone organic compounds include 2,4-dihydroxybenzophenone, 2- Examples of the benzophenone include hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3H2O, 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. Other oligomer and polymer type compounds having a benzophenone structure can also be used.

[0168] More specifically, KEMISORB 10, 11, 11S manufactured by Chemipro Chemical Co., Ltd. 12, 111, SEESORB manufactured by Shipro Chemical Co., Ltd. 101, 107, ADE Co., Ltd. Examples include ADK STAB 1413 manufactured by KA Corporation and UV-12 manufactured by Sun Chemical Co., Ltd.

[0169] Examples of the salicylic acid ester organic compound include phenyl salicylate, p-octylphenyl salicylate, t-butylphenyl salicylate, etc. In addition, oligomer type and polymer type compounds having a salicylic acid ester structure can also be used.

[0170] <Antioxidants (L)> 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 can increase 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.

[0171] The "antioxidant" in the present invention may be any compound having a radical scavenging function or a peroxide decomposing function, and specifically, examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds, and known antioxidants can be used. In addition, the antioxidant used in the present invention is preferably one that does not contain a halogen atom.

[0172] Among these antioxidants, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, preferred ones include hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants.

[0173] Hindered phenol antioxidants include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]Undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di -t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4 ,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylene bisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, Examples include 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, etc. In addition, oligomer type and polymer type compounds having a hindered phenol structure can also be used.

[0174] More specifically, examples of the polyurethane foam include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA CORPORATION; KEMINOX101, 179, 76, and 9425 manufactured by Chemipro Corporation; IRGANOX1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Ltd.; and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Co., Ltd.

[0175] Examples of hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butane tetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butane tetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, and 1,2,2,6,6-pentamethyl-4-piperidyl tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensation product of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1- Ester of piperidineethanol with 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl)ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5-bi 1,2,2,6,6-pentamethyl-4-pyridyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-Hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc. In addition, oligomer type and polymer type compounds having a hindered amine structure can also be used.

[0176] More specifically, examples of the antibacterial agents include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION; KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemical Co., Ltd.; Tinuvin 249, TINUVIN 111FDL, 123, 144, 292, and 5100 manufactured by BASF Corporation; and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Co., Ltd.

[0177] Examples of phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono( 2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphonite, tris(tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylide diphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl Examples include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethyl bis(2,4-di-t-butyl-6-methylphenyl) phosphite, etc. Other oligomer and polymer type compounds having a phosphite structure can also be used.

[0178] More specifically, examples of the polymerizable compound include ADK STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA CORPORATION, IRGAFOS168 manufactured by BASF Corporation, and HostanoxP-EPQ manufactured by Clariant Chemicals K.K.

[0179] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, etc. In addition, oligomer and polymer type compounds having a thioether structure can also be used.

[0180] More specifically, examples thereof include ADK STAB AO-412S and AO-503 manufactured by ADEKA CORPORATION, and KEMINOXPLS manufactured by Chemipro Chemicals Co., Ltd.

[0181] These antioxidants may be used alone or in combination of two or more kinds in any ratio as required.

[0182] Furthermore, when the content of the antioxidant is 0.5 to 5.0% by mass relative to 100% by mass of the solid content of the coloring composition, the transmittance, spectral characteristics, and sensitivity are excellent, which is more preferable.

[0183] <Leveling agent (M)> In order to improve the coating property of the composition on a transparent substrate and the drying property of the colored coating, it is preferable to add a leveling agent to the photosensitive coloring composition of the present invention. As the leveling agent, various surfactants such as silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used.

[0184] Examples of silicone surfactants include linear polymers formed from siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or ends.

[0185] More specifically, examples of the 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 Co., Ltd., and FZ-7002 and 2110 manufactured by Dow Corning Toray Co., Ltd. , 2122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341.

[0186] The fluorosurfactant may be a surfactant or a leveling agent having a fluorocarbon chain.

[0187] More specifically, examples of the resins include Surflon S-242, S-243, S-420, S-611, S-651, and S-386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation; FC-4430 and FC-4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; and Ftergent 602A manufactured by NEOS Corporation.

[0188] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. , sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamines, alkyl alkanolamides, alkyl imidazolines, and the like.

[0189] More specifically, Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, and L manufactured by Kao Corporation are S-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, LATEMURU PD-420, PD-430, PD-430S, PD450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L1 06, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amit 102, 105, Examples of such copolymers include 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA CORPORATION, and (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0190] Examples of the cationic surfactant include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0191] More specifically, examples of the concentrate include Acetamine 24, Cortamine 24P, 60W, and 86P, all of which are manufactured by Kao Corporation.

[0192] Examples of the anionic surfactant include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkyl naphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates.

[0193] More specifically, examples of the antibacterial agent include Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adekacol TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

[0194] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyl dimethyl amino acetate betaine, and alkyl amine oxides such as lauryl dimethyl amine oxide. Some examples include:

[0195] More specifically, examples of such an agent include Anhithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N manufactured by Kao Corporation.

[0196] When the photosensitive coloring composition of the present invention contains a surfactant, the amount of the surfactant added is preferably 0.001 to 2.0 mass %, more preferably 0.005 to 1.0 mass %, based on the total solid content of the composition of the present invention. Within this range, the coloring composition has a good balance between the coatability, pattern adhesion, and transmittance. The photosensitive coloring composition of the present invention may contain only one type of surfactant, or may contain two or more types. When two or more types are contained, the total amount is preferably within the above range.

[0197] <Storage stabilizer (N)> The coloring composition of the present invention can contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenyl, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the coloring agent (100% by mass).

[0198] <Adhesion improver (O)> The photosensitive coloring composition of the present invention can contain an adhesion improver such as a silane coupling agent in order to improve adhesion to the substrate. By improving the adhesion with the adhesion improver, the reproducibility of fine lines is improved and the resolution is improved.

[0199] Examples of the adhesion improver 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 and N-2-(aminoethyl)-3- Examples of the silane coupling agent include aminosilanes such as aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride salt of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, sulfides such as bis(triethoxysilylpropyl)tetrasulfide, and isocyanates such as 3-isocyanatepropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, relative to 100 parts by mass of the colorant in the coloring composition. Within this range, the effect is greater, and a good balance of adhesion, resolution, and sensitivity is achieved, which is more preferable.

[0200] <Method of producing colored composition> The coloring composition of the present invention includes a pigment, a dispersant, a binder resin, and / or a solvent, Preferably, the pigments can be produced by finely dispersing them together with a dispersing aid (a dye derivative or a surfactant) using various dispersing means such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, an attritor, etc. At this time, two or more types of pigments may be dispersed simultaneously in the colorant carrier, or they may be dispersed separately in the pigment carrier and then mixed.

[0201] <Pigment dispersion particle size> The average dispersed particle diameter of the pigment in the coloring composition is preferably in the range of 30 to 200 nm, more preferably in the range of 40 to 120 nm. In this range, the viscosity and dispersion stability are high, and when this coloring composition is used alone or in mixtures and a photopolymerizable material is further added, a photosensitive coloring composition having not only high viscosity and dispersion stability but also high sensitivity and high development speed can be obtained, and when a color filter is produced using this, a high-quality color filter can be obtained.

[0202] The method for measuring the dispersed particle size of pigments is to use Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle transparency set to absorption mode, particle shape set to non-spherical, and D50 set to the average diameter. The dilution solvent used for the measurement is the same as that used for the dispersion, and it is preferable to measure samples treated with ultrasound immediately after sample preparation, as this tends to give results with less variation.

[0203] <Method for producing photosensitive coloring composition> In addition, when used as a photosensitive coloring composition, it can be prepared as a solvent-developable or alkali-developable coloring composition. The solvent-developable or alkali-developable coloring composition can be prepared by mixing the coloring composition, a photopolymerizable monomer and / or a photopolymerization initiator, and, if necessary, a solvent, other dispersing aids, and additives. The photopolymerization initiator may be added at the stage of preparing the coloring composition, or may be added later to the prepared coloring composition.

[0204] <Solvent> The coloring composition of the present invention contains a solvent to facilitate the formation of a colored film by coating the composition on a substrate such as glass so that the dry film thickness is 0.2 to 5 μm. The solvent is selected in consideration of the good coatability of the coloring composition, the solubility of each component of the coloring composition, and safety.

[0205] As the solvent, any solvent commonly used in the relevant field can be used, and they are used alone or in combination as appropriate according to the coating conditions (speed, drying conditions, etc.) taking into consideration performance such as boiling point, SP value, evaporation rate, and viscosity.

[0206] Examples of the solvent to be used include ester solvents (solvents containing -COO- but not -O- in the molecule), ether solvents (solvents containing -O- but not -COO- in the molecule), ether ester solvents (solvents containing -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.

[0207] Examples of ester solvents include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0208] Ether solvents include ethylene glycol monomethyl ether, ethylene glycol Monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, dipropylene glycol dimethyl ether, dipropylene glycol methyl-n-propyl ether, anisole Examples include phenetole, methyl anisole, etc.

[0209] Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl ... Examples of the butyl acetate acetate include butyl acetate, ...

[0210] Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0211] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, 1,3-butylene glycol, and glycerin.

[0212] Aromatic hydrocarbon solvents include benzene, toluene, xylene, mesitylene, and the like.

[0213] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone. These solvents may be used alone or in combination of two or more kinds.

[0214] Of the above solvents, from the viewpoint of coatability and drying property, it is preferable to include an organic solvent having a boiling point at 1 atm of 120° C. or more and 180° C. or less. Among them, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are more preferred.

[0215] <Removal of large particles> The 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, filtration with a sintered filter or membrane filter, etc. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

[0216] <Color filters> Next, the color filter of the present invention will be described. The color filter of the present invention comprises a red filter segment, a green filter segment, and a blue filter segment, and may further comprise a magenta filter segment, a cyan filter segment, and a yellow filter segment.

[0217] <Manufacturing method of color filters> The color filter can be manufactured by a printing method or a photolithography method. The formation of filter segments by the printing method can be patterned simply by repeatedly printing and drying a colored composition prepared as a printing ink, and is therefore a low-cost and mass-productive method for producing color filters. Furthermore, the development of printing technology has made it possible to print fine patterns with high dimensional accuracy and smoothness. In order to print, it is preferable to use a composition that does not allow the ink to dry or solidify on the printing plate or blanket. In addition, control of the fluidity of the ink on the printing machine is also important, and the ink viscosity can be adjusted by using a dispersant or an extender pigment.

[0218] When the filter segment is formed by the photolithography method, the coloring composition prepared as the above-mentioned solvent-developable or alkali-developable colored resist material is applied to a transparent substrate by a coating method such as spray coating, spin coating, slit coating, or roll coating so that the dry film thickness is 0.2 to 5 μm. If necessary, the dried film is exposed (irradiated with radiation) through a mask having a predetermined pattern that is provided in contact with or not in contact with the film. Thereafter, the uncured portion is removed by immersing in a solvent or an alkali developer or spraying the developer by a spray or the like to form a desired pattern, and the same operation is repeated for other colors to produce a color filter. Furthermore, heating can be performed as necessary to promote polymerization of the colored resist material. According to the photolithography method, a color filter with higher accuracy than the above-mentioned printing method can be produced.

[0219] In the development, an aqueous solution of sodium carbonate, sodium hydroxide, etc. is used as an alkaline developer, and an organic alkali such as dimethylbenzylamine, triethanolamine, etc. can also be used. In addition, a defoaming agent or a surfactant can also be added to the developer. In order to increase the exposure sensitivity, after the colored resist is applied and dried, a water-soluble or alkaline water-soluble resin, such as polyvinyl alcohol or a water-soluble acrylic resin, may be applied and dried to form a film for preventing polymerization inhibition due to oxygen, and then exposure may be performed.

[0220] The color filter of the present invention can be manufactured by the above-mentioned method, as well as by an electrodeposition method, a transfer method, an inkjet method, etc., and the coloring composition of the present invention can be used for any of these methods. The electrodeposition method is a method for manufacturing a color filter by utilizing a transparent conductive film formed on a substrate and electrodepositing each color filter segment on the transparent conductive film by electrophoresis of colloidal particles. The transfer method is a method in which filter segments are formed in advance on the surface of a peelable transfer base sheet, and the filter segments are transferred to a desired substrate. It is law.

[0221] Before forming each color filter segment on a transparent substrate or a reflective substrate, a black matrix can be formed in advance. As the black matrix, a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, or a resin film with a light-shielding agent dispersed therein can be used, but is not limited to these. Also, a thin film transistor (TFT) can be formed in advance on the transparent substrate or the reflective substrate, and then each color filter segment can be formed. Also, an overcoat film, a transparent conductive film, or the like can be formed on the color filter of the present invention as necessary.

[0222] The color filter of the present invention is laminated to an opposing substrate using a sealant, liquid crystal is injected through an injection port provided in the sealing part, the injection port is sealed, and a polarizing film or a retardation film is laminated to the outside of the substrate as necessary, to produce a color liquid crystal display device. This color liquid crystal display device can be used in liquid crystal display modes that use color filters such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertically aligned (VA), and optically convencive bend (OCB).

[0223] Furthermore, the color filter of the present invention can be used for producing color solid-state imaging devices, organic EL displays, quantum dot displays, electronic paper, and the like, in addition to color liquid crystal displays.

[0224] <Liquid crystal display device> A liquid crystal display device equipped with the color filter of the present invention will now be described. The liquid crystal display device of the present invention comprises the color filter of the present invention and a light source. Examples of light sources include cold cathode fluorescent lamps (CCFL) and white LEDs, but in the present invention, it is preferable to use a white LED because it broadens the red reproduction range. Figure 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with the color filter of the present invention. The device 10 shown in Figure 1 comprises a pair of transparent substrates 11 and 21 arranged to face each other with a space therebetween, and liquid crystal LC is sealed between them.

[0225] 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.

[0226] 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).

[0227] 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.

[0228] 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.

[0229] 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, 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.

[0230] 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).

[0231] 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.

[0232] 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.

[0233] The white LED light source may be one in which a fluorescent filter is formed on the surface of a blue LED, or one in which a fluorescent material is contained in the resin package of a blue LED, 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. In particular, 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 is preferred.

[0234] 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.).

[0235] Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D (manufactured by Nichia Chemical Industries, Ltd.). EXAMPLES

[0236] The present invention will be described below with reference to examples. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively.

[0237] Before describing the examples, each measurement method will be described.

[0238] Resin weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), The min value (mgKOH / g) is as follows:

[0239] (Average molecular weight of resin) The number average molecular weight (Mn) and weight average molecular weight (Mw) of the binder 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, a THF solution was used as the eluent, and the measurements were performed at a flow rate of 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.

[0240] (Acid value of resin (mgKOH / g)) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of the 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 solid content of the resin was calculated from the acid value of the resin solution and the solid content concentration of the resin solution.

[0241] (Amine value of basic resin type dispersant) The amine value of the basic resin-type dispersant is the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 and converted into solid content.

[0242] <Production of fine phthalocyanine pigment> (Fine Phthalocyanine Pigments A-1 to A-5) According to the examples of JP2017-111398A, fine phthalocyanine pigments (A-1 to A-5) of the following formulas 51 to 55 were produced. The structures are shown below.

[0243] (Fine Phthalocyanine Pigment A-1) Formula (51) [ka]

[0244] (Fine Phthalocyanine Pigment A-2) Formula (52) [ka]

[0245] (Fine Phthalocyanine Pigment A-3) Formula (53) [ka]

[0246] (Fine Phthalocyanine Pigment A-4) Formula (54) [ka]

[0247] (Fine Phthalocyanine Pigment A-5) Formula (55) [ka]

[0248] (Fine Phthalocyanine Pigment (A-6)) Phthalocyanine pigment CI Pigment Green 58 (DIC "FASTGEN GREEN A110"), 1200 parts of sodium chloride, and diethylene glycol 120 parts of Licor were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded for 6 hours at 70° C. This kneaded product was added to 3000 parts of warm water, heated to 70° C. and stirred for 1 hour to form a slurry, which was filtered and repeatedly washed with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. for one day to obtain 97 parts of a fine phthalocyanine pigment (A-6).

[0249] (Fine Phthalocyanine Pigment (A-7)) The fine phthalocyanine pigment (A-1) and the fine phthalocyanine pigment (A-6) were mixed in equal amounts to obtain a fine phthalocyanine pigment (A-7).

[0250] (Fine Phthalocyanine Pigment (A-8)) 200 parts of phthalocyanine pigment CI Pigment Green 36, 14 parts of sodium chloride 00 parts of ethylene glycol and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80°C for 6 hours. Next, the kneaded product was poured into 8 liters of warm water. The mixture was heated to 80°C and stirred for 2 hours to form a slurry, which was then filtered and repeatedly washed with water to remove sodium chloride and diethylene glycol, and then dried at 85°C overnight to obtain 190 parts of a fine phthalocyanine pigment (A-8).

[0251] (Fine Phthalocyanine Pigment (A-9)) In a 300 mL flask, 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 74 parts of bromine were charged. The mixture was heated to 130°C over 40 hours, taken out in water, and filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged in a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out in 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A-9). The resulting finely divided phthalocyanine pigment (A-9) was found to be a halogenated zinc phthalocyanine pigment having an average of 13.97 halogen atoms per molecule, including an average of 11.46 bromine atoms and an average of 2.51 chlorine atoms, as determined by X-ray fluorescence analysis using a Rigaku ZSX100E.

[0252] (Fine Phthalocyanine Pigment (A-10)) In a 300 mL flask, 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 59 parts of bromine were charged. The mixture was heated to 130°C over 40 hours, taken out in water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged in a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out in 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A-10). The obtained fine phthalocyanine pigment (A-10) was found to have an average of 12.71 halogen atoms per molecule from fluorescent X-ray analysis, of which the average number of bromine atoms was 10.22 and the average number of chlorine atoms was 2.49, making it a halogenated zinc phthalocyanine pigment.

[0253] (Fine Phthalocyanine Pigment (A-11)) In a 300 mL flask, 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 44 parts of bromine were charged. The mixture was heated to 130°C over 40 hours, taken out in water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged in a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out in 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A-11). The obtained fine phthalocyanine pigment (A-11) was found to have an average of 11.98 halogen atoms per molecule from fluorescent X-ray analysis, of which the average number of bromine atoms was 9.00 and the average number of chlorine atoms was 2.98, making it a halogenated zinc phthalocyanine pigment.

[0254] (Fine Phthalocyanine Pigment (A-12)) In a 300 mL flask, 109 parts of sulfuryl chloride, 131 parts of aluminum chloride, 18 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 52 parts of bromine were charged. The mixture was heated to 130°C over 40 hours, taken out in water, and then filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged in a 1 L double-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out in 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A-12). The obtained fine phthalocyanine pigment (A-12) was found to have an average of 12.69 halogen atoms per molecule from fluorescent X-ray analysis, of which the average number of bromine atoms was 8.54 and the average number of chlorine atoms was 4.16, making it a halogenated zinc phthalocyanine pigment.

[0255] (Fine Phthalocyanine Pigment (A-13)) In a 300 mL flask, 91 parts of sulfuryl chloride, 72 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 29 parts of bromine were charged. The temperature was raised to 130°C for 40 hours. The mixture was heated over a period of 10 minutes, taken out in water, and filtered to obtain a green crude pigment. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol, and 1.8 parts of xylene were charged into a 1L twin-arm kneader and kneaded at 100°C for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80°C, stirred for 1 hour, filtered, washed with hot water, dried, and pulverized to obtain a fine phthalocyanine pigment (A-13). The obtained fine phthalocyanine pigment (A-13) was found by fluorescent X-ray analysis to have an average of 8.88 halogen atoms per molecule, of which the average number of bromine atoms was 6.90, and the average number of chlorine atoms was 1.98, making it a halogenated zinc phthalocyanine pigment.

[0256] <Production of fine yellow pigment> (Fine yellow pigments (a-1 to 3)) According to the examples of JP 2012-226110 A, fine phthalocyanine pigments (a-1 to a-3) of quinophthalone pigments represented by the following formulas (56) to (58) were prepared. The structures are shown below.

[0257] (Fine yellow pigment a-1) Formula (56) [ka]

[0258] (Fine yellow pigment a-2) Formula (57) [ka]

[0259] (Fine yellow pigment a-3) Formula (58) [ka]

[0260] (Fine Yellow Pigment (a-4)) CI Pigment Yellow 138 (PY138) (BASF "Paliothol Yellow" 100 parts of ethylene glycol (Law K0960-HD), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80°C for 6 hours. This mixture was poured into 2000 parts of warm water, heated to 80°C and stirred for 1 hour to form a slurry, which was filtered and washed repeatedly with water to remove the salt and solvent, and then dried at 80°C for one day and night to obtain 95 parts of finely divided yellow pigment (a-4).

[0261] (Fine Yellow Pigment (a-5)) 100 parts of isoindoline yellow pigment CI Pigment Yellow 139 (Ciba Japan Co., Ltd. "Irgaphor Yellow 2R-CF"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader and kneaded for 10 hours at 60°C. Next, this mixture was poured into 3 liters of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, which was filtered and washed repeatedly to remove sodium chloride and the solvent, and then dried at 80°C for one day and night to obtain a fine yellow pigment (a-5).

[0262] (Fine Yellow Pigment (a-6)) Metal complex yellow pigment (CI Pigment Yellow 150, manufactured by LANXESS) 100 parts of "Yellow Pigment E4GN", 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 10 hours. Next, this mixture was poured into 3 liters of warm water, 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 sodium chloride and the solvent, and then dried at 80°C for one day and night to obtain a finely divided yellow pigment (a-6). The average primary particle size was 36.6 nm.

[0263] (Fine Yellow Pigment (a-7)) 500 parts of yellow pigment CI Pigment Yellow 185 (Ciba Japan "Paliotol Yellow D1155"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader and kneaded for 8 hours at 120° C. Next, this kneaded mixture was poured into 5 liters of warm water and stirred for 1 hour while heating to 70° C. to form a slurry. After repeatedly filtering and washing with water to remove the sodium chloride and diethylene glycol, the mixture was dried at 80° C. for a day and night to obtain a finely divided yellow pigment (a-7).

[0264] <Dye derivative (b)> The following dye derivatives were used: Pigment derivative (b-1) [ka] Pc represents a phthalocyanine skeleton.

[0265] Pigment derivative (b-2) [ka]

[0266] <Preparation of Basic Resin-Type Dispersant (B1) Solution> (Basic resin type dispersant (B1-1) solution) In a reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer, 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 133 parts of PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to start polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the non-volatile content. Next, 61 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were charged into the reactor, and the reaction was continued by stirring while maintaining 110°C under a nitrogen atmosphere. Two hours after the addition, the polymerization solution was sampled and the solid content was measured, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more based on the non-volatile content. The reaction solution was cooled to room temperature to stop the polymerization. As a result of GPC measurement, the mass average molecular weight of the polymer was 20000, the molecular weight distribution Mw / Mn was 1.4, and the reaction conversion rate was 98.5%. In this way, a basic resin type dispersant (B1-1) with an amine value of 169.8 mg KOH / g per solid content was obtained. After cooling to room temperature, about 2 g of the resin type dispersant solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and propylene glycol monomethyl ether acetate (PGMAc) was added to the previously synthesized basic resin type dispersant (B1-1) so that the non-volatile content was 20 mass% to prepare a basic resin type dispersant (B1-1) solution.

[0267] (Basic resin type dispersant (B1-2) solution) A reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer was charged with 133 parts of PGMAc, and the temperature was raised to 110°C while replacing with nitrogen. A dropping vessel was charged with 177 parts of diethylaminoethyl methacrylate, 3 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of PGMAc, and 6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and after stirring until homogeneous, the mixture was dropped into the reaction vessel over 2 hours, and the reaction was continued at the same temperature for 3 hours. In this way, a basic resin-type dispersant (B1-2) with an amine value of 345mgKOH / g per solid content and a number average molecular weight (Mn) of 3000 was obtained. The solution was diluted in the same manner as the resin-type dispersant (B1-1) solution to prepare a basic resin-type dispersant (B1-2) solution.

[0268] (Basic resin type dispersant (B1-3) solution) A reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer was charged with 133 parts of PGMAc, and the temperature was raised to 110°C while replacing with nitrogen. A dropping vessel was charged with 177 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate, 3 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of PGMAc, and 6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and after stirring until homogeneous, the mixture was dropped into the reaction vessel over 2 hours, and the reaction was continued at the same temperature for 3 hours. In this way, a basic resin type dispersant (B1-3) with an amine value of 201 mgKOH / g per solid content and a number average molecular weight of 3,800 (Mn) was obtained. The solution was diluted in the same manner as the basic resin type dispersant (B1-1) solution to prepare a basic resin type dispersant (B1-3) solution.

[0269] (Basic resin type dispersant (B1-4) solution) In a flask equipped with a condenser and a stirrer, 1.0 parts by mass of AIBN and 186 parts by mass of propylene glycol monomethyl ether acetate were charged, followed by 27 parts by mass of methyl methacrylate, 27 parts by mass of butyl methacrylate, 19 parts by mass of 2-ethylhexyl methacrylate, 16 parts by mass of benzyl methacrylate, 16 parts by mass of triethylene glycol ethyl ether methacrylate, and 3.6 parts by mass of cumyl dithiobenzoate, and the atmosphere was replaced with nitrogen for 30 minutes. After that, the temperature of the reaction solution was raised to 60°C with gentle stirring, and this temperature was maintained for 24 hours to carry out living radical polymerization. Next, to this reaction solution was added a solution in which 1.0 part by mass of AIBN and 54 parts by mass of dimethylaminoethyl methacrylate were dissolved in 108 parts by mass of propylene glycol monomethyl ether acetate and nitrogen substitution was performed for 30 minutes, and living radical polymerization was performed at 60°C for 24 hours. Thereafter, the mixture was diluted in the same manner as the basic resin type dispersant (B1-1) solution to prepare a basic resin type dispersant (B1-4) solution.

[0270] (Basic resin type dispersant (B1-5) solution) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 500 parts of methyl methacrylate, 22 parts of thioglycerol, and 511 parts of propylene glycol monomethyl ether acetate were charged, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 90°C, and 0.50 parts of AIBN were added, followed by reaction for 7 hours. After confirming that 95% had reacted by measuring the non-volatile content, the mixture was cooled to room temperature to obtain a 50% non-volatile solution of a vinyl polymer having a weight average molecular weight of 5200 and two free hydroxyl groups at one end region. Next, 90.4 parts of isophorone diisocyanate, 45.1 parts of propylene glycol monomethyl ether acetate, and 0.11 parts of dibutyltin dilaurate as a catalyst were charged, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 100°C, reacted for 3 hours, and then cooled to 40°C to obtain a prepolymer solution having an isocyanate group. 22.2 parts of methyliminobispropylamine, 13.2 parts of dibutylamine, and 304.6 parts of propylene glycol monomethyl ether acetate were charged into a reaction vessel 2 equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, and heated to 100°C. The prepolymer solution was added dropwise thereto over 30 minutes, and the reaction was continued for another hour, after which the reaction was terminated by cooling to room temperature. If necessary, a portion of the solvent was removed by distillation under reduced pressure, and then the mixture was diluted in the same manner as the basic resin type dispersant (B1-1) solution to prepare a basic resin type dispersant (B1-5) solution.

[0271] (Basic resin type dispersant (B1-6) solution) In a reaction apparatus equipped with a gas inlet tube, a condenser, an agitator, and a thermometer, 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110°C under a nitrogen stream to initiate polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more based on the nonvolatile content. Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (Hitachi Chemical Co., Ltd., Fancryl FA-711MM) as a second block (A block) monomer were added to the reactor, and the reaction was continued by stirring while maintaining the temperature at 110°C under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidyl methacrylate, a sample of the polymerization solution was taken and the nonvolatile content was measured. It was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more based on the nonvolatile content, and the reaction solution was cooled to room temperature to terminate the polymerization. In this way, a basic group resin-type dispersant (B1-6) having a piperidyl skeleton and an amine value per nonvolatile content of 57 mg KOH / g and a number average molecular weight of 4,500 (Mn) was obtained. A basic-group resin-type dispersant (B1-6) solution was prepared by diluting in the same manner as the resin-type dispersant (B1-1) solution.

[0272] (Basic resin type dispersant (B1-7) solution) The method for producing the pigment dispersant (1) described in Production Example 1 of Japanese Patent No. 5513691 includes the step of: A basic-based resin-type dispersant (B1-7) solution was prepared by diluting a quaternary acrylate copolymer (23 / 77 wt%) (quaternary methacrylate copolymer (23 / 77 wt%); quaternary methacrylate ratio 27 mol%) in the same manner as for the resin-type dispersant (B1-1) solution.

[0273] (Preparation of Carboxylic Acid Resin Dispersant (B2) Solution) (Preparation of Carboxylic Acid Resin Dispersant (B2-1) Solution) A reaction vessel equipped with a gas inlet tube, a temperature controller, a condenser, and a stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc, and substituted with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts of 2,2'-azobisisobutyronitrile and 90 parts of PGMAc was added and reacted for 7 hours. It was confirmed that 95% had reacted by measuring the solid content. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by acid value measurement, and PGMAc was added to dilute the solution so that the solid content was 20% by solid content measurement, obtaining a resin-type dispersant (B2-1) solution with an acid value of 70 mgKOH / g and a weight average molecular weight of 8,500.

[0274] (Preparation of Carboxylic Acid Resin Dispersant (B2-1-1) Solution) A reaction vessel equipped with a gas inlet tube, a condenser, an agitator, and a thermometer was charged with 3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of PGMAc, and 0.1 parts of dimethylbenzylamine. After replacing the atmosphere with nitrogen gas, the reaction vessel was heated to 120°C and reacted for 4 hours, and then at 80°C for 2 hours. Further, 30 parts of tertiary butyl acrylate, ETERNACOLL OXMA (methacrylic acid (3-ethyl oxalate), The reactor was charged with 20 parts of methyl 2,2'-dimethyl ether (Ube Industries), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of PGMAc, and while maintaining the temperature inside the reactor at 80°C, 0.2 parts of 2,2'-azobisisobutyronitrile was added in 15 increments every 30 minutes. One hour after the final addition, the non-volatile content was measured, and it was confirmed that 95% of the monomer had reacted. PGMAc was added to dilute the mixture so that the non-volatile content was 20%. A carboxylic acid resin dispersant (BMA) with an acid value of 51 mgKOH / g per non-volatile content and a weight average molecular weight (Mw) of 24,000 was added. 2-1-1) A solution was obtained.

[0275] (Preparation of Carboxylic Acid Resin Dispersant (B2-1-2) Solution) 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 solid 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 solid content that 95% 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 solid content was adjusted with PGMAc to obtain a carboxylic acid-based resin-type dispersant (B2-1-2) solution with a solid content of 20%. The acid value of the obtained dispersant was 68, the unsaturated double bond equivalent was 1593, and the weight average molecular weight was 13000.

[0276] (Preparation of Carboxylic Acid Resin Dispersant (B2-2) Solution) 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 solid 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. A carboxylic acid-based resin-type dispersant (B2-2) solution with a solid content of 20% was obtained by adjusting the solid content with PGMAc. The obtained dispersant was a white solid at room temperature and had an acid value of 49 mg KOH / g.

[0277] <Production example of binder resin (C)> (Preparation of binder resin (C2-1) liquid) With reference to the <Synthesis of Resin A> in JP 2004-361455 A, some of the materials used were changed and the following preparation was performed. Into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube, 145 g of propylene glycol monomethyl ether acetate was introduced, and the atmosphere in the flask was changed from air to nitrogen. After that, the temperature was raised to 110°C, and a solution of 7.6 g of t-butyl hydroperoxide added to a monomer mixture consisting of 73.7 g (0.4 mol) of 2-ethylhexyl acrylate (2-EHA), 71 g (0.5 mol) of glycidyl methacrylate (GMA), and 22 g (0.1 mol) of tricyclodecane-based monomethacrylate (dicyclopentanyl methacrylate (DCPMA) Hitachi Chemical Co., Ltd. FA-513M) was added dropwise to the flask from the dropping funnel over a period of 2 hours, and stirring was continued for another 2 hours at 100°C. (The above is the first step.) Next, the atmosphere in the flask was changed from nitrogen to air, and 36.0 g [0.5 mol, (100 mol% relative to the glycidyl group of the glycidyl methacrylate used in this reaction)] of acrylic acid (AA), 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone were added to the flask, and the reaction was continued for 6 hours at 110°C, and was terminated when the solid acid value reached 1 mgKOH / g. (The above is the second step.) Next, 53.2 g (0.35 mol) of tetrahydrophthalic anhydride and 0.8 g of triethylamine were added, and the reaction was continued for 3.5 hours at 120°C. (The above is the third step.) Finally, the binder resin (C2-1) liquid was diluted with propylene glycol monomethyl ether acetate to a solid content of 20 mass%. (The above is the fourth step.)

[0278] (Preparation of binder resin (C2-2 to C2-7) liquid) Except for using the materials in Table 1, binder resin liquids (C2-2 to C2-7) were prepared in the same manner as for the binder resin liquid (C2-1).

[0279] (Preparation of binder resin (C1-1 to C1-3) liquid) By carrying out only the first and fourth steps in the preparation of binder resin (C2-1) liquid using the materials in Table 1, binder resin (C1-1 to 3) liquids were prepared.

[0280] [Table 1]

[0281] The abbreviations in Table 1 are as follows: PGMAC: Propylene glycol monomethyl ether acetate 2-EHA: 2-Ethylhexyl acrylate SMA: Stearyl methacrylate 2-EHMA: 2-Ethylhexyl methacrylate MMA: Methyl methacrylate St: styrene AA: Acrylic acid DCPMA: dicyclopentanyl methacrylate IBMA: Isobornyl methacrylate GMA: glycidyl methacrylate THPA: Tetrahydrophthalic anhydride

[0282] <Method for producing colored composition (single color)> [Example 1] (Preparation of Coloring Composition (R-1)) The mixture below was stirred and mixed until homogeneous, and then dispersed in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours. The mixture was then filtered through a filter with a pore size of 5.0 μm to produce a colored composition (R-1) with a non-volatile content of 24.3% by mass. Pigment (A-2): 20.0 parts Basic resin type dispersant ((B1-1): 20% non-volatile liquid): 2.5 parts Acidic resin type dispersant ((B2-1): 20% non-volatile liquid): 2.5 parts Binder resin (C1-1: 20% non-volatile liquid): 20.0 parts Solvent (P): 55.0 parts

[0283] [Examples 2 to 32, Comparative Examples 1 to 2] (Preparation of Colored Compositions (R-2 to R-34)) Colored compositions (R-2 to 34) were prepared in the same manner as in Example 1, except that the material types and masses were changed as shown in Table 2.

[0284] [Table 2]

[0285] <Evaluation of Coloring Composition> The obtained colored compositions (R-1 to 34) were subjected to tests for viscosity and storage stability by the following methods. The test results are shown in Table 3. The meaning of the evaluation rank is as follows: ◎: Very good 〇: Good △: Practical ×: Not suitable for practical use

[0286] (Measurement of Viscosity Characteristics) The viscosity was measured at a rotation speed of 20 rpm using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) and the evaluation rank is as follows. ○: Viscosity 4.0 or more and less than 20.0 ×: Viscosity 20 or more (Storage stability) The colored compositions obtained in the Examples and Comparative Examples were evaluated for storage stability by the following method. The initial viscosity on the day after the preparation of the colored composition and the viscosity over time accelerated at 40°C for one week were measured using an E-type viscometer ("ELD type viscometer" manufactured by Toki Sangyo Co., Ltd.) at 25°C and a rotation speed of 50 rpm. From the initial viscosity and viscosity over time values, the rate of change in viscosity over time was calculated using the following formula, and the storage stability was evaluated in two stages. [Change in viscosity over time] = |([Initial viscosity] - [Viscosity over time]) / [Initial viscosity]| x 100 ○: Change rate is less than 5% ×: Change rate of 5% or more

[0287] (Foreign matter evaluation) For the foreign matter evaluation, the colored composition was applied to a transparent substrate so that the dried coating thickness was about 2.0 μm, and the coating substrate was heat-treated in an oven at 230°C for 1 hour to count the number of foreign matters in the coating. The evaluation was performed by observing the surface using a metal microscope "BX60" (manufactured by Olympus Systems Co., Ltd.). The magnification was 500 times, and the number of foreign matters observable in any five visual fields in transmission was counted. The evaluation criteria are as follows. ◎: The number of foreign objects is less than 5 〇: The number of foreign objects is 5 or more and less than 20 △: The number of foreign objects is 21 or more and less than 100. ×: 100 or more foreign objects

[0288] [Table 3]

[0289] <Method for producing photosensitive coloring composition> [Example 101] (Photosensitive coloring composition (X-1)) The following raw materials were mixed and stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition (X -1). Coloring composition (R-1: non-volatile content 25%): 75.0 parts Binder resin (C2-1: non-volatile content 20%): 5.0 parts Thermosetting compound (CE-1): 0.5 part Thermosetting compound (CE-2): 0.5 part Photopolymerizable monomer (D): 2.0 parts Photopolymerization initiator (E): 1.8 parts Sensitizer (H): 0.2 parts Thiol chain transfer agent (I): 0.4 parts Polymerization inhibitor (J): 0.1 parts UV absorber (K): 0.1 parts Antioxidant (L): 0.1 parts Leveling agent (M: non-volatile content 3%): 1.0 part Storage stabilizer (N): 0.1 parts Silane coupling agent (O): 0.2 parts Solvent (P): 13.0 parts

[0290] [Examples 102 to 139, Comparative Examples 101 to 102] (Preparation of Photosensitive Coloring Compositions (X-2 to 41)) Photosensitive coloring compositions (X-2 to 41) were prepared in the same manner as in Example 101, except that the coloring composition and the binder resin solution of Example 101 were changed as shown in Table 4. The raw materials for each were as follows. In this specification, Examples 135 and 138 are reference examples.

[0291] [Table 4]

[0292] <Thermosetting compound (CE)> Epoxy compound (CE-1) (CE-1-1) 1,2-2,2'-bis(hydroxymethyl)-1-butanol Epoxy-4-(2-oxiranyl)cyclohexane adduct [EHPE-3150 (manufactured by Daicel)], (CE-1-2) Glycidyl etherified epoxy compounds of sorbitol [Denacol EX611 (manufactured by Nagase ChemteX Corporation)] (CE-1-3) Triglycidyl isocyanurate Equal amounts of (CE-1-1) to (CE-1-3) were mixed to prepare an epoxy compound (CE-1). Oxetane compounds (CE-2): 3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane [Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

[0293] <Polymerizable compound (D)> (D-1) Trimethylolpropane triacrylate [Aronix M309 (manufactured by Toagosei Co., Ltd.)] (D-2) Dipentaerythritol penta- and hexaacrylate (E-2) [Aronix M402 (manufactured by Toagosei Co., Ltd.)] (D-3) Polybasic acidic acrylic oligomer [Aronix M520 (manufactured by Toagosei Co., Ltd.)] (D-4) Caprolactone-modified dipentaerythritol hexaacrylate [KAYARAD DPCA-30 (manufactured by Nippon Kayaku)]

[0294] (D-5) Multifunctional urethane acrylate Pentaerythritol triacrylate (432 g) and hexamethylene diisocyanate (84 g) were charged into a 1-liter five-necked reaction vessel and reacted at 60°C for 8 hours to obtain a product containing a multifunctional urethane acrylate (D-5) having a (meth)acryloyl group. The proportion of the multifunctional urethane acrylate (D-5) in the product was 70 mass%, with the remainder being other photopolymerizable monomers. It was confirmed by IR analysis that no isocyanate groups were present in the reaction product.

[0295] (D-6) Bifunctional bisphenol A (meth)acrylate [ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)] (D-7) Ethoxylated isocyanuric acid triacrylate [A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)] The above (D-1) to (D-7) were mixed in equal amounts to prepare a photopolymerizable monomer (D).

[0296] <Photopolymerization initiator (E)> (E-1) 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Irgacure 907 (BASF Japan)] (E-2) 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Irgacure 379 (BASF Japan)] (E-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [Lucirin TPO (manufactured by Ciba Japan)] (E-4) 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl 1,2'-biimidazole [Biimidazole (Kurokane Chemicals)] (E-5) p-Dimethylaminoacetophenone [DMA (manufactured by Daikifine)] (E-6) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime) [Irgacure OXE02 (manufactured by BASF Japan)] (E-7) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2- Methyl-1-propan-1-one [Irgacure 2959 (BASF Japan)] (E-8) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Irgacure 819 (BASF Japan)] The above (E-1) to (E-8) were mixed in equal amounts to prepare a photopolymerization initiator (E).

[0297] <Sensitizer (H)> (H-1) 2,4-Diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku)] (H-2) 4,4'-Bis(diethylamino)benzophenone [CHEMARK DEABP (manufactured by Chemark Chemical)] The above (H-1) and (H-2) were mixed in equal amounts to prepare sensitizer (H).

[0298] <Thiol-based chain transfer agents (I)> (I-1) Trimethylolethane tris(3-mercaptobutyrate) [TEMB (Showa Denko)] (I-2) Trimethylolpropane tris(3-mercaptobutyrate) [TPMB (Showa Denko)] (I-3) Pentaerythritol tetrakis(3-mercaptopropionate) [PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (I-4) Trimethylolpropane tris(3-mercaptopropionate) [TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (I-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate [TEMPIC (Sakai Chemical Industry Co., Ltd.)] The above (I-1) to (I-5) were mixed in equal amounts to prepare a thiol-based chain transfer agent (I).

[0299] <Polymerization inhibitor (J)> (J-1) 3-Methylcatechol (J-2) Methylhydroquinone (J-3) t-Butylhydroquinone The above (J-1) to (J-3) were mixed in equal amounts to prepare a polymerization inhibitor (J).

[0300] <Ultraviolet absorber (K)> (K-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)] (K-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN900 (manufactured by BASF Japan)] The above (K-1) to (K-2) were mixed in equal amounts to prepare an ultraviolet absorber (K).

[0301] <Antioxidants (L)> (L-1) Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (L-2) Dioctadecyl 3,3'-thiodipropanoate (L-3) Tris[2,4-di-(t)-butylphenyl]phosphine (L-4) Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (L-5) p-Octylphenyl Salicylate The above (L-1) to (L-5) were mixed in equal amounts to prepare an antioxidant (L).

[0302] <Leveling agent (M)> 1 copy of "BYK-330" manufactured by BYK-Chemie, 1 copy of "Megafac F-551" manufactured by DIC Corporation, 1 copy of "Emulgen 103" manufactured by Kao Corporation A mixed solution of 97 parts of PGMAc.

[0303] <Storage stabilizer (N)> (N-1) 2,6-bis(1,1-dimethylethyl)-4-methylphenol (Honshu Chemical Industry Co., Ltd. "BHT") (N-2) Triphenylphosphine (“TPP” manufactured by Hokuko Chemical Industry Co., Ltd.) The above (N-1) to (N-2) were mixed in equal amounts to prepare a storage stabilizer (N).

[0304] <Adhesion improver (O)> (O-1) 3-Glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (O-2) 3-Methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (O-3) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (O-4) 3-Mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)] The above (O-1) to (O-4) were mixed in equal amounts to prepare a silane coupling agent (O).

[0305] <Solvent (P)> (P-1) PGMAc 30 copies (P-2) Cyclohexanone 30 parts (P-3) Ethyl 3-ethoxypropionate 10 parts (P-4) Propylene glycol monomethyl ether 10 parts (P-5) Cyclohexanol acetate 10 parts (P-6) Dipropylene glycol methyl ether acetate 10 parts The above (P-1) to (P-6) were mixed in the above-mentioned parts by mass to prepare a solvent (P).

[0306] <Evaluation of Photosensitive Coloring Composition> Each test was carried out according to the following method, and the test results are shown in Table 5. The meaning of the evaluation rank is as follows: ◎: Very good 〇: Good △: Practical ×: Not suitable for practical use

[0307] <Evaluation of photosensitive coloring composition for color filters> The photosensitive coloring compositions for color filters obtained in the Examples and Comparative Examples were evaluated for development residue, linearity, taper shape, chemical resistance, and storage stability by the following methods. The results are shown in Tables 5 and 6.

[0308] <Formation of filter segments> A black matrix was patterned on a 100 mm x 100 mm, 0.7 mm thick glass substrate, the obtained photosensitive coloring composition was applied onto the substrate using a spin coater, and the substrate was dried at 90°C for 90 seconds to remove the solvent, obtaining a coating film having a thickness of 2.4 μm. Next, the coating film was irradiated with 100 mJ / cm using an ultra-high pressure mercury lamp through a photomask having a predetermined pattern. 2 The coating 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 parts and form the desired pattern. The resulting coating was heat-treated in an oven at 230°C for 20 minutes to form a filter segment. The coating thickness was measured using Dektak3030 (manufactured by Japan Vacuum Engineering Co., Ltd.).

[0309] <Development residue> The obtained filter segments were checked for the presence or absence of development residues using a microscope (Olympus Optical Co., Ltd. "BX-51") The remaining area of ​​residues in a square pixel with a 50 μm × 50 μm hollow was calculated and evaluated as follows. ◎: No residue ○: 100μm 2 less than △: 100μm 2 More than 500μm 2 less than ×:500μm 2 End

[0310] <Pattern linearity> The pattern linearity of the obtained filter segment was confirmed by a scanning electron microscope (Hitachi High-Tech Corporation's "S-3000H") and evaluated as follows: ◎: Very good linearity ○: Good linearity ×: The more the tapered part becomes wavy, the poorer the linearity.

[0311] <Taper angle> The pattern shape of the obtained filter segment was confirmed with a scanning electron microscope (Hitachi High-Tech's "S-3000H"). The evaluation was carried out by capturing an SEM image of a 100 μm-wide stripe pattern, and evaluating the angle of the tapered portion using a protractor as follows: ⊚: Good tapered shape (taper angle of 40° or more and less than 70°) ○: Practical taper shape (taper angle is 20° or more and less than 40°, or 70° or more and less than 90°) ×: Poor taper shape (taper angle less than 20° or more than 90°)

[0312] (Foreign matter evaluation) For the foreign matter evaluation, the photosensitive coloring composition was applied to a transparent substrate so that the dry coating thickness was about 2.0 μm, and the coating substrate was heat-treated in an oven at 230°C for 1 hour to count the number of foreign matters in the coating. The evaluation was performed by observing the surface using a metal microscope "BX60" (manufactured by Olympus Systems Co., Ltd.). The magnification was 500 times, and the number of foreign matters observable in any five visual fields in transmission was counted. The evaluation criteria were as follows. ◎: The number of foreign objects is less than 5 〇: The number of foreign objects is 5 or more and less than 20 △: The number of foreign objects is 21 or more and less than 100. ×: 100 or more foreign objects

[0313] (Solvent resistance evaluation) The photosensitive coloring composition was applied onto a transparent substrate so that the dry coating thickness was about 2.0 μm, and the substrate obtained by heat treatment at 230°C for 1 hour in an oven was immersed in an N-methylpyrrolidone solution for 30 minutes, washed with ion-exchanged water, air-dried, and the pattern in the 100 μm photomask portion was observed using an optical microscope and evaluated. The evaluation ranks are as follows. ○: Appearance and color are good with no change △: Some wrinkles, etc., occur, but the color remains unchanged and in good condition ×: Peeling or discoloration occurs

[0314] [Table 5] [Explanation of symbols]

[0315] 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

Claims

1. A coloring composition comprising an organic pigment (A), a resin-type dispersant (B), and a binder resin (C), wherein the organic pigment (A) comprises at least one pigment selected from the group consisting of a zinc phthalocyanine pigment (A1) and an aluminum phthalocyanine pigment (A2), and The resin-type dispersant (B) comprises a basic resin-type dispersant (B1), The binder resin (C) contains a copolymer of a monomer (CL) having a homopolymer glass transition temperature of less than 0° C. and a monomer (CH) having a homopolymer glass transition temperature of 150° C. or higher, The monomer (CL) is a monomer selected from the group consisting of n-butyl acrylate, isoamyl acrylate, 2-ethylhexyl acrylate, and lauryl methacrylate; The monomer (CH) comprises a monomer selected from the group consisting of dicyclopentanyl methacrylate, isobornyl methacrylate, adamantyl acrylate, and adamantyl methacrylate; A coloring composition characterized in that the monomer (CL) is 1 to 99 mass % and the monomer (CH) is 1 to 50 mass % (excluding 4.7 mass % or less) of the total monomers.

2. 2. The colored composition according to claim 1, wherein the binder resin (C) is a non-photosensitive alkali-soluble resin (C1) and / or a photosensitive alkali-soluble resin (C2).

3. 3. The colored composition according to claim 1, wherein the binder resin (C) has a glass transition temperature calculated from the following formula (2) of 100° C. or lower. Formula (2) Fox formula 1 / Tg=W １ / Tg １ +W ２ / Tg ２ +・・・+W ｎ / Tg ｎ (However, １ From W ｎ indicates the weight fraction of the n monomers used, and Tg １ From Tg ｎ indicates the glass transition temperature (unit: absolute temperature "K") of a homopolymer (a single polymer of a monomer). In the case of a photosensitive alkali-soluble resin (C2), calculation is performed for the monomer constituting the main chain. When there are multiple binder resins, the glass transition temperature of each binder resin is calculated using formula (2), and then the glass transition temperature of the entire binder resin is calculated using formula (2) again. W in the second calculation １ From W ｎ indicates the weight fraction of each binder resin, and Tg １ From Tg ｎ indicates the glass transition temperature of each binder resin (unit: absolute temperature "K").

4. The coloring composition according to any one of claims 1 to 3, wherein the resin type dispersant (B) contains 5 to 50 parts by mass of the basic resin type dispersant (B1) relative to 100 parts by mass of the binder resin (C).

5. The colored composition according to any one of claims 1 to 4, wherein the resin-type dispersant (B) contains an acidic resin-type dispersant (B2).

6. 6. The coloring composition according to claim 1, wherein the organic pigment (A) contains a yellow pigment (a).

7. A photosensitive coloring composition comprising the coloring composition according to any one of claims 1 to 6, a polymerizable compound (D), and a photopolymerization initiator (E).

8. A color filter formed using the photosensitive coloring composition according to claim 7.

9. A liquid crystal display device comprising the color filter according to claim 8.

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