Photosensitive coloring composition for color filter used in solid-state imaging device, color filter, and solid-state imaging device

Abstract

To provide a coloring composition with high sensitivity and excellent developability even when a lot of pigments are included, a color filter having suitable spectral transmittance of visible light by using them, and a solid-state imaging device.SOLUTION: The photosensitive coloring composition for color filters used in solid-state imaging devices contains a coloring agent (A), a resin-type dispersant (B), a polymerizable compound (C), a photoinitiator (D), and an organic solvent. The coloring agent (A) contains a phthalocyanine pigment (A1), a quinophthalone pigment (A2), and a metal azo pigment (A3), and the coloring agent (A) is contained by 50 wt.% or more and 90 wt.% or less of the total solid content of the coloring composition.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a photosensitive coloring composition for a color filter used in a solid-state imaging device, and to a color filter and a solid-state imaging device. [Background technology]

[0002] In solid-state imaging devices, as devices become smaller, there is a demand for thinner color films in the color filters used as components thereof, and it is becoming difficult to achieve the desired chromaticity unless the pigment concentration in the film is increased. This has created a need for fine pigments, and the finer the pigment, the more important it is to have highly functional dispersants (pigment derivatives, resins with dispersing properties, etc.).

[0003] A dispersant is adsorbed onto a pigment or via a pigment derivative, and Patent Document 1 discloses a technology that uses a combination of a polar moiety with low solvent affinity and a resin with high solvent affinity.

[0004] In addition to dispersants, advanced techniques are also required for the selection of pigment types, composition ratios, and other materials that contribute to photosensitivity in order to achieve the required spectral characteristics. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2014-202774 A Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention aims to provide a coloring composition that has high sensitivity and excellent developability even when it contains a large amount of pigment, and a color filter and a solid-state imaging device that have suitable spectral transmittance of visible light by using the same. [Means for solving the problem]

[0007] The present invention relates to a photosensitive coloring composition for color filters used in solid-state imaging devices, which comprises a colorant (A), a resin-type dispersant (B), a polymerizable compound (C), a photopolymerization initiator (D) and an organic solvent, wherein the colorant (A) comprises a phthalocyanine pigment (A1), a quinophthalone pigment (A2) and a metal azo pigment (A3), and the colorant (A) accounts for 50% by weight or more and 90% by weight or less of the total solid content of the coloring composition.

[0008] The present invention also relates to a photosensitive coloring composition for color filters used in the above solid-state imaging device, characterized in that the resin-type dispersant (B) contains a basic resin-type dispersant (B1), and the amine value of the basic resin-type dispersant (B1) is 10 to 80 mgKOH / g.

[0009] The present invention also relates to a photosensitive coloring composition for color filters used in the above-mentioned solid-state imaging device, characterized in that the polymerizable compound (C) comprises a polymerizable compound (C1) having four or more ethylenically unsaturated double bonds, and the polymerizable compound (C1) having four or more ethylenically unsaturated double bonds is 1% by weight or more and 15% by weight or less in the total solid content of the photosensitive coloring composition.

[0010] The present invention also relates to a photosensitive coloring composition for color filters used in the above solid-state imaging device, characterized in that it further contains a binder resin (E) having a weight average molecular weight (Mw) of 12,000 or less (excluding the case where the binder resin is a resin-type dispersant (B)).

[0011] The present invention also relates to a color filter for use in a solid-state imaging device, comprising a layer formed from the photosensitive coloring composition for a color filter used in the solid-state imaging device.

[0012] The present invention also relates to a solid-state imaging device comprising the above color filter. Effect of the Invention

[0013] According to the present invention, it is possible to provide a photosensitive coloring composition for color filters used in solid-state imaging devices that has high sensitivity and excellent developability even when it contains a large amount of pigment, and by using the same, it is possible to provide a color filter and a solid-state imaging device that have suitable spectral transmittance of visible light. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0014] The terms used in this specification are defined below. When "(meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" is written, it means "acryloyl and / or methacryl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide", respectively, unless otherwise specified. In this specification, "CI" means Color Index (CI).

[0015] The photosensitive coloring composition for color filters used in the solid-state imaging device of the present invention contains a colorant (A), a resin-type dispersant (B), a photopolymerizable monomer (C), a photopolymerization initiator (D) and an organic solvent.

[0016] <Colorant (A)> The colorant (A) in the present invention is characterized in that it contains a halogenated phthalocyanine pigment (A1), a quinophthalone pigment (A2), and a metal azo pigment (A3), and the colorant (A) is contained in an amount of 50% by weight or more and 90% by weight or less of the total solid content of the coloring composition. Even at a high pigment concentration where the colorant (A) is contained in an amount of 50% by weight or more and 90% by weight or less of the total solid content of the coloring composition, by containing the halogenated phthalocyanine pigment (A1), the quinophthalone pigment (A2), and the metal azo pigment (A3), it is possible to increase the transmittance in the central region of the visible light wavelength and decrease the transmittance in the left and right regions of the visible light wavelength, and to obtain suitable green spectral characteristics.

[0017] <Phthalocyanine pigment (A1)> The phthalocyanine pigment (A1) used in the present invention is a compound having a phthalocyanine skeleton, and preferably has a central metal which may be substituted. The phthalocyanine skeleton may have a substituent such as a halogen atom such as chlorine or bromine. The central metal which may be substituted is preferably copper, zinc, aluminum, nickel, vanadium, or a compound containing these metals.

[0018] For example, CI Pigment Green 36, 58, 59, 62, 63, and pigments described in JP-A-2017-111398 can be mentioned, but are not limited thereto. Among these, from the viewpoint of transmittance, CI Pigment Green 36, 58, 59, 62, 63, and pigments described in JP-A-2017-111398 are preferably mentioned. Particularly preferably usable are CI Pigment Green 36 and 58.

[0019] <Quinophthalone pigments (A2)> Examples of the quinophthalone pigment (A2) used in the present invention include CI Pigment Yellow 138, 231, and 233, and pigments described in JP-A-2012-226110.

[0020] <Metallic azo pigment (A3)> Examples of the metal azo pigment (A3) used in the present invention include CI Pigment Yellow 150 and pigments described in JP-A-2016-180100, JP-A-2017-171915, and JP-A-2018-021204.

[0021] (Other pigments) The colorant (A) may be used in combination with colorants other than the phthalocyanine pigment (A1), the quinophthalone pigment (A2), and the metal azo pigment (A3) to the extent that the required optical properties are not impaired. Examples of such colorants include other known organic pigments, inorganic pigments, dyes, etc.

[0022] Specific examples of other green pigments that can be used in combination include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 37, 45, 48, 50, 51, 54, and 55.

[0023] 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, 11 6, 117, 118, 119, 120, 123, 126, 127, 128, 129, 139, 147, 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, etc.

[0024] Furthermore, blue pigments, red pigments and purple pigments can also be added to the extent that they do not impair the effects of the present invention.

[0025] Examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, synthetic iron black, etc. Inorganic pigments are used in combination with organic pigments to ensure good coatability, sensitivity, developability, etc. while maintaining a balance between saturation and brightness.

[0026] <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. can be used. In addition, derivatives of these dyes or lake pigments obtained by making dyes into lakes may also be used. Representative dyes have an acidic group or a basic group in the pigment structure.

[0027] 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.

[0028] In the case of a basic dye, it can be used after being salted 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, and it is more preferred to use a salt-forming compound obtained by salting a basic dye with 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, a cyano-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or an acid dye.

[0029] Furthermore, when the dye structure has a polymerizable unsaturated group, the dye can be made to have excellent durability, which is preferable.

[0030] Examples of the dye structure 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.

[0031] 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.

[0032] <Minification of pigments> The method for micronizing the pigment used in the coloring composition of the present invention is not particularly limited, and for example, any of wet grinding, dry grinding, and dissolution precipitation methods can be used. As exemplified in the present invention, the pigment can be micronized by salt milling treatment using a kneader method, which is a type of wet grinding. 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.

[0033] 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.

[0034] As the water-soluble inorganic salt, sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc. can be used, but sodium chloride (table salt) is preferred from the viewpoint of cost. 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.

[0035] 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.

[0036] 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.

[0037] <Metal Removal> If a specific metal element is present in a large amount in the coloring composition as an impurity other than the pigment component, it may hinder the dispersion stability over time, and may cause a decrease in heat resistance or a decrease in sensitivity. In addition, a color filter made using this may have foreign matter, which may result in a decrease in brightness. The total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) contained in the photosensitive coloring composition is preferably 500 mass ppm or less.

[0038] The total amount of specific metal elements contained in the photosensitive coloring composition is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less.The lower limit of the total amount of specific metal elements is not particularly limited, but is preferably 1 mass ppm or more, more preferably 5 mass ppm or more.Within the above range, it is possible to obtain a photosensitive coloring composition that can form a color filter that can suppress costs, has excellent storage stability, and has little generation of foreign matter and little decrease in brightness.

[0039] The amount of each specific metal element contained in the photosensitive coloring composition is preferably 100 ppm by mass or less, and more preferably 50 ppm by mass or less.

[0040] In addition, it is also preferable that the amount of impurities that do not function effectively, such as metals such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co that constitute the pigment, is small, and these can be removed in the same manner as the specific metal elements by the following method. Furthermore, it is also preferable that Mn, Cs, Ti, Co, Si, Pd, etc., that are mixed in by materials (such as catalysts) used in the manufacturing process of various raw materials for the photosensitive coloring composition, are low in concentration.

[0041] Methods for removing the colorant (A) or metals that have become mixed in from equipment during the manufacturing process include methods using water washing as described in JP-A-2010-83997, JP-A-2018-36521, JP-A-7-198928, JP-A-8-333521, JP-A-2009-7432, etc., and methods for removing magnetic foreign matter using a magnet as described in JP-A-2011-48736, and the like. One or more of these methods can be used as appropriate.

[0042] The content of specific metal elements can be measured by inductively coupled plasma emission spectrometry (ICP).

[0043] <Dye derivatives> In the coloring composition, a dye derivative can be used as necessary. The dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Examples of the dye derivative include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphoric acid group, as well as amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group. Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0044] Specifically, diketopyrrolopyrrole dye derivatives are described in JP 2001-220520 A, WO 2009 / 081930 B, WO 2011 / 052617 B, WO 2012 / 102399 B, and JP 2017-156397 A; phthalocyanine dye derivatives are described in JP 2007-226161 A, WO 2016 / 163351 B, JP 2017-165820 B, and Japanese Patent No. 5753266 A; and anthraquinone dye derivatives are described in 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 are disclosed in JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383; dioxazine dye derivatives are disclosed in JP-A-2011-162662; thiazine indigo dye derivatives are disclosed in JP-A-2007-3147 85, triazine-based dye derivatives are disclosed in JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, and JP-A-2007-314681, benzoisoindole-based dye derivatives are disclosed in JP-A-2009-57478, quinophthalone-based dye derivatives are disclosed in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2007-314681. 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, and JP-A-2005-213404. In these documents, the dye derivative may be referred to as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as 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.

[0045] These dye derivatives can be used alone or in combination of two or more kinds.

[0046] The dye derivative is added in an amount of preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass, per 100 parts by mass of the pigment.

[0047] By adding a dye derivative to a pigment and carrying out a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, or solvent salt milling, the dye derivative is adsorbed onto the pigment surface, and the primary particles of the pigment can be made finer than when the dye derivative is not added.

[0048] By adding a dye derivative to a pigment and carrying out a dispersion treatment such as wet dispersion using a two-roll roller, a three-roll roller, or beads, the dye derivative is adsorbed onto the pigment surface, the pigment surface has polarity, and adsorption of the resin-type dispersant is promoted, and compatibility with the pigment, the dye derivative, the resin-type dispersant, the solvent, and other additives is improved, and the dispersion stability and viscosity stability over time when the composition is made into a colored composition or a colored curable composition are improved. In addition, the improved compatibility provides excellent stability over time of the coating film when the colored curable composition is applied to a glass substrate, etc., and the stability and characteristics dependency of the pattern shape on the waiting time from application of the colored curable composition to exposure (PCD: Post Coating Delay) and the waiting time from exposure to heat treatment (PED: Post Exposure Delay) and the line width sensitivity stability are improved. In addition, by adsorbing and covering the pigment surface with the dye derivative and the resin-type dispersant, it is possible to suppress the aggregation of the pigment and the crystal precipitation due to sublimation when the coating film is heated and baked. Furthermore, the variation in development time and development residue are also suppressed.

[0049] <Resin-type dispersant (B)> A known resin-type dispersant can be used in the photosensitive coloring composition of the present invention. The resin-type dispersant may be any dispersant that has a colorant affinity site that has the property of adsorbing to an added colorant and a site that is compatible with a colorant carrier, and that functions to adsorb to an added colorant and stabilize the dispersion in the colorant carrier. Specifically, urethane-based dispersants such as polyurethane, polycarboxylates such as polyacrylates, unsaturated polyamides, polycarboxylates, polycarboxylate (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl-containing polycarboxylates, and modified products thereof. Examples of the dispersants that can be used include oil-based dispersants such as amides formed by the reaction of poly(lower alkylene imine) with a polyester having a free carboxyl group or salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyester-based compounds, modified polyacrylate-based compounds, ethylene oxide / propylene oxide adducts, and phosphate-based compounds, and these can be used alone or in combination of two or more types.

[0050] The resin type dispersant (B) preferably contains a basic resin type dispersant (B1), and from the viewpoint of dispersion stability, the basic resin type dispersant (B1) preferably has an amine value of 10 to 80 mgKOH / g.

[0051] <Basic resin type dispersant (B1)> Preferred examples of the basic resin-type dispersant (B1) include nitrogen-atom-containing graft copolymers, and nitrogen-atom-containing acrylic block copolymers and urethane-based polymer dispersants having functional groups including tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc. in the side chains.

[0052] As disclosed in JP 2009-185277 A, a preferred example is the combined use of a resin-type dispersant having an aromatic carboxyl group and a vinyl resin having a tertiary amino group (having the function of a resin-type dispersant).

[0053] <Acidic resin type dispersant (B2)> Preferred examples of the acidic resin-type dispersant (B2) include resin-type dispersants having an aromatic carboxylic acid structure, which can be produced by known methods such as those described in WO2008 / 007776, JP2008-029901A, JP2009-155406A, JP2010-185934A, JP2011-157416A, JP2009-251481A, JP2007-23195A, and JP1996-143651A.

[0054] The resin type dispersant (B) is preferably used in an amount of about 3 to 200% by mass based on the total amount of the colorant, and from the viewpoint of film-forming properties, more preferably about 5 to 100% by mass.

[0055] <Polymerizable compound (C)> The photosensitive coloring composition of the present invention includes a coloring composition, a polymerizable compound, and a photopolymerization initiator. The polymerizable compound includes a monomer or oligomer that is cured by ultraviolet light, heat, or the like to form a transparent resin.

[0056] Examples of the polymerizable compound include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, Examples of the acrylic acid esters and methacrylic acid esters include pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylic acid ester of methylolated melamine, epoxy (meth)acrylate, and urethane acrylate, as well as (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinyl formamide, and acrylonitrile.

[0057] (Polymerizable compound having an acid group) The polymerizable compound may contain a photopolymerizable monomer having an acid group, such as a sulfonic acid group, a carboxyl group, or a phosphoric acid group.

[0058] Examples of photopolymerizable monomers having an acid group include esters of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid with dicarboxylic acids; esters of polycarboxylic acids with monohydroxyalkyl (meth)acrylates; and the like. Specific examples include free carboxyl group-containing monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates, such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, with dicarboxylic acids, such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and free carboxyl group-containing oligoesters of tricarboxylic acids, such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid, with monohydroxy monoacrylates or monohydroxy monomethacrylates, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0059] (Polymerizable compound having urethane bond) The polymerizable compound may contain a monomer having an ethylenically unsaturated bond and a urethane bond. Examples of the monomer include a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and a polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and further reacting the alcohol with a (meth)acrylate having a hydroxyl group.

[0060] 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.

[0061] Examples of the polyfunctional isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

[0062] The polymerizable compound includes a polymerizable compound (C1) having four or more ethylenically unsaturated double bonds, and the polymerizable compound (C1) having four or more ethylenically unsaturated double bonds is preferably 1% by weight or more and 15% by weight or less in the total solid content of the photosensitive coloring composition from the viewpoint of sensitivity.

[0063] The polymerizable compounds can be used alone or in combination of two or more kinds.

[0064] The blending amount of the polymerizable compound is preferably 1 to 50 mass %, more preferably 2 to 40 mass parts, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is blended, the curability and developability are further improved.

[0065] <Photopolymerization initiator (D)> The photopolymerization initiator (D) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4- acetophenone compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzil dimethyl ketal; benzophenone, benzoylbenzoic acid, benzoylbenzoic acid methyl, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t- butylperoxycarbonyl)benzophenone and other benzophenone compounds; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, 2,4-diethylthioxanthone and other thioxanthone compounds; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis( triazine-based compounds such as 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Examples of suitable oxime ester compounds include 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; or titanocene compounds. Among these, oxime ester compounds are preferred.

[0066] The photopolymerization initiator (D) can be used alone or in combination of two or more kinds.

[0067] (Oxime ester compounds) In the oxime ester compound, the NO bond of the oxime is cleaved by absorbing ultraviolet light, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, so that 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 curing of the coating film may decrease, but oxime ester compounds are preferably used because they have high quantum efficiency.

[0068] Examples of the oxime ester compound include oxime ester photopolymerization initiators described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, and JP-A-2018-116258.

[0069] The content of the photopolymerization initiator (D) 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. When an appropriate amount is added, the photocurability and developability are further improved.

[0070] <Binder resin (E)> The coloring composition of the present invention preferably contains a binder resin (E). The binder resin is a resin having a transmittance of 80% or more in the entire wavelength region of 400 to 700 nm. The transmittance is preferably 95% or more. In terms of curability, the binder resin may be, for example, a thermoplastic resin, a thermosetting resin, or an active energy ray curable resin. The active energy ray curable resin may have an active energy ray reactive functional group in the thermoplastic resin or the thermosetting resin. In terms of physical properties, the binder resin is preferably an alkali-soluble resin from the viewpoint of developability. The alkali solubility is for imparting development solubility in the alkali development step during the production of a color filter, and an acidic group is required. In addition, even if it is prescribed as a binder resin (E), if it cannot be distinguished from the resin-type dispersant (B) in terms of the wording, it is treated as the resin-type dispersant (B).

[0071] The weight average molecular weight (Mw) of the binder resin (E) in the present invention is 2,000 to 40,000, preferably 3,000 to 30,000, more preferably 12,000 or less, in order to impart solubility in alkaline development. 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, and the exposed pattern is less likely to remain. If it exceeds 40,000, the solubility in alkaline development decreases, residue is generated, and the linearity of the pattern deteriorates.

[0072] The binder resin (E) can be used alone or in combination of two or more kinds.

[0073] The content of the binder resin (E) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on 100 parts by mass of the colorant. When an appropriate amount is contained, a coating can be easily formed and good color characteristics can be easily obtained.

[0074] <Thermoplastic resin> Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins. Examples of the alkali-soluble thermoplastic resin include resins having an acidic group such as a carboxyl group or a sulfonic group. Examples of the alkali-soluble thermoplastic resin include acrylic resins having an acidic group, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, and isobutylene / maleic acid (anhydride) copolymers. Among these, acrylic resins having an acidic group and styrene / styrene sulfonic acid copolymers are preferred in terms of improving developability, heat resistance, and transparency.

[0075] <Active energy ray-curable alkali-soluble resin> The active energy ray-curable alkali-soluble resin preferably has an ethylenically unsaturated double bond. The ethylenically unsaturated double bond can be introduced, for example, by the following methods (i) and (ii). The resin is three-dimensionally crosslinked by the effect of active energy rays, increasing the crosslink density and improving chemical resistance.

[0076] [Method (i)] In the method (i), for example, an ethylenically unsaturated monomer having an epoxy group is copolymerized with another monomer to obtain a copolymer, and a carboxyl group of an unsaturated monobasic acid having an ethylenically unsaturated double bond is subjected to an addition reaction with the side chain epoxy group of the copolymer.Then, a polybasic acid anhydride is reacted with the generated hydroxyl group to introduce an ethylenically unsaturated double bond and a carboxyl group.

[0077] 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. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with unsaturated monobasic acids.

[0078] 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.

[0079] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. 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.

[0080] Examples of other monomers include the following: (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, and ethoxypolyethylene glycol (meth)acrylate; Alternatively, examples of the monomer include (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, and acryloylmorpholine; styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acid vinyls such as vinyl acetate and vinyl propionate.

[0081] 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-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide N-substituted maleimides such as N-substituted maleimides such as N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide and 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of para-cumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol.

[0082] 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 another monomer, thereby introducing an ethylenically unsaturated double bond and a carboxyl group.

[0083] [Method (ii)] Method (ii) is a method in which an isocyanate group of an ethylenically unsaturated monomer having an isocyanate group is reacted with a side chain hydroxyl group of a copolymer obtained by copolymerizing an ethylenically unsaturated monomer having a hydroxyl group with another monomer.

[0084] Examples of the ethylenically unsaturated monomer 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, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to hydroxyalkyl(meth)acrylates, and polyester mono(meth)acrylates obtained by addition of poly(γ-valerolactone), poly(ε-caprolactone, and / or poly(12-hydroxystearic acid). 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.

[0085] 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.

[0086] Examples of other monomers that can constitute the alkali-soluble resin include, in addition to the other ethylenically unsaturated monomers already described, N-substituted maleimides, alkyleneoxy group-containing monomers, phosphate group-containing ethylenically unsaturated monomers, carboxyl group-containing ethylenically unsaturated monomers, and the like. Examples of N-substituted maleimides include cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-( 2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimide acridine and the like. Examples of the alkyleneoxy group-containing monomer include 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.

[0087] As the carboxyl group-containing ethylenically unsaturated monomer, the monomers already explained can be used.

[0088] The phosphate group-containing ethylenically unsaturated monomer is, for example, a compound obtained by reacting the hydroxyl group of the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0089] <Alkali-soluble resin having no ethylenically unsaturated double bond> The coloring composition of the present invention can contain an alkali-soluble resin having no ethylenically unsaturated double bond in order to adjust the degree of hardening of the coating.

[0090] The acid value of the alkali-soluble resin in the present invention is 50 to 200 (KOH mg / g) in order to impart solubility in alkaline development, preferably 70 to 180, more preferably 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 the acid value exceeds 200, adhesion to the substrate decreases, making it difficult to leave an exposed pattern.

[0091] Each of the raw materials used in the synthesis of the binder resin can be used alone or in combination of two or more kinds.

[0092] <Thermosetting compounds> In the present invention, a thermosetting compound can be further included in combination with the thermoplastic resin as a binder resin. When a color filter is produced using the coloring composition for color filters of the present invention, the inclusion of a thermosetting compound reacts during firing of the filter segment to increase the crosslink density of the coating film, thereby improving the heat resistance of the filter segment, suppressing pigment aggregation during firing of the filter segment, and improving the contrast ratio.

[0093] 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.

[0094] <Sensitizer> 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, 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, and other polymethine dyes, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyrazinoporphyrazine derivatives. , phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenyl glyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0095] 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.

[0096] 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.

[0097] The sensitizers can be used alone or in combination of two or more kinds.

[0098] The content of the sensitizer is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator. When an appropriate amount is contained, the curability and developability are further improved.

[0099] <Thiol-based chain transfer agents> 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.

[0100] 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.

[0101] 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.

[0102] The thiol chain transfer agents can be used alone or in combination of two or more kinds.

[0103] The content of the thiol chain transfer agent is preferably 0.1 to 10 mass%, more preferably 0.1 to 3 mass%, based on 100 mass% of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the photosensitivity and taper shape are improved, and wrinkles are less likely to occur on the coating surface.

[0104] <Polymerization inhibitor> The photosensitive coloring composition may contain a polymerization inhibitor, which can suppress photosensitivity due to diffracted light from a mask during exposure in a photolithography method, making it easier to obtain a pattern of a desired shape.

[0105] Examples of the polymerization inhibitor include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-tert-butyl catechol, 3-tert-butyl catechol, 4-tert-butyl catechol, and 3,5-di-tert-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol, and 2-n- alkyl resorcinol compounds such as butyl resorcinol, 4-n-butyl resorcinol, 2-tert-butyl resorcinol, and 4-tert-butyl resorcinol; alkyl hydroquinone compounds such as methyl hydroquinone, ethyl hydroquinone, propyl hydroquinone, tert-butyl hydroquinone, and 2,5-di-tert-butyl hydroquinone; phosphine compounds such as tributyl phosphine, trioctyl phosphine, tricyclohexyl phosphine, triphenyl phosphine, and tribenzyl phosphine; phosphine oxide compounds such as trioctyl phosphine oxide and triphenyl phosphine oxide; phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite; pyrogallol; and phloroglucine.

[0106] The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. Within this range, the effect of the polymerization inhibitor is increased, and the linearity of the taper, wrinkles in the coating film, pattern resolution, etc. are improved.

[0107] <Ultraviolet absorbing agent> 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 compounds, triazine-based compounds, benzophenone-based compounds, salicylic acid ester-based compounds, cyanoacrylate-based compounds, and salicylate-based compounds.

[0108] The content of the ultraviolet absorber is preferably 5 to 70% by mass relative to 100% by mass of the total of the photopolymerization initiator and the ultraviolet absorber. When an appropriate amount is contained, the resolution after development is further improved.

[0109] The total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the adhesion between the substrate and the coating is further improved, and good resolution can be obtained.

[0110] Benzotriazole compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α, α-Dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side and linear alkyl ester mixture, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300 reaction products, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t- Butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate. Other oligomer and polymer type compounds having a benzotriazole structure can also be used.

[0111] Triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of the compound include 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. In addition, oligomer and polymer type compounds having a triazine structure can also be used.

[0112] Benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc. In addition, oligomer type and polymer type compounds having a benzophenone structure can also be used.

[0113] Examples of the salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc. In addition, oligomer-type and polymer-type compounds having a salicylate structure can also be used.

[0114] <Antioxidants> The photosensitive coloring composition of the present invention can contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the photosensitive coloring composition from being oxidized and yellowed by the thermal process during thermal curing or ITO annealing, and therefore can improve the transmittance of the coating film. In particular, when the colorant concentration of the coloring composition is high, the amount of the coating film crosslinking component is reduced, so that a highly sensitive crosslinking component is used or the amount of the photopolymerization initiator is increased, resulting in a phenomenon in which yellowing during the thermal process becomes stronger. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a high transmittance of the coating film can be obtained.

[0115] Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present invention, the antioxidant is preferably a compound that does not contain a halogen atom.

[0116] Among these, from the viewpoint of achieving both the transmittance and the sensitivity of the coating film, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0117] The antioxidants can be used alone or in combination of two or more kinds.

[0118] 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 colored composition, the transmittance, spectral characteristics, and sensitivity are excellent, which is more preferable.

[0119] <Leveling agent> 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.

[0120] 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.

[0121] <Storage stabilizer> 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 tetraphenylphosphine, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10% by mass based on the total amount of the coloring agent (100% by mass).

[0122] <Adhesion improver> 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.

[0123] 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 large, and a good balance of adhesion, resolution, and sensitivity is achieved, which is more preferable.

[0124] <Organic solvent> The coloring composition of the present invention contains an organic solvent in order to easily form 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 organic solvent is selected in consideration of the good coatability of the coloring composition, the solubility of each component of the coloring composition, and safety.

[0125] As the organic 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.

[0126] Examples of the organic 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.

[0127] Of the above organic 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, diethylene glycol diethyl ether, N,N-dimethylformamide, N-methylpyrrolidone, etc. are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, tripropylene glycol methyl ether, etc. are more preferred.

[0128] <Method for producing photosensitive composition> The photosensitive coloring composition included in the present invention can be produced by finely dispersing a colorant in a colorant carrier such as a dispersant or binder resin and / or a solvent, preferably together with a dispersion aid (dye derivative or 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, or an attritor (colorant dispersion). At this time, two or more types of colorants may be dispersed simultaneously in a colorant carrier, or may be mixed with those dispersed separately in a colorant carrier. When the solubility of a colorant such as a dye is high, specifically, when the solubility is high in the solvent used, and the colorant is dissolved by stirring and no foreign matter is confirmed, it is not necessary to produce the colorant by fine dispersion as described above.

[0129] In addition, when the photosensitive coloring composition for color filters is used as a resist material, 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 colorant dispersion, the photopolymerizable monomer and / or the photopolymerization initiator, and, if necessary, a solvent, other dispersion 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.

[0130] <Removal of large particles> The photosensitive coloring composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means of centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or a membrane filter, etc. In this way, it is preferable that the coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, the particles are 0.3 μm or less.

[0131] <Water content in color composition> The photosensitive coloring composition of the present invention preferably has a water content of 2 mass % or less.

[0132] When the water content of the photosensitive coloring composition is within the above range, the composition is excellent in dispersion stability and sensitivity even after storage over time.

[0133] The water content in the photosensitive coloring composition is preferably 1.8% by mass or less, and more preferably 1.6% by mass or less. If the water content is sufficiently low within this range, problems with dispersion stability and sensitivity are unlikely to occur even after storage over time.

[0134] The method for controlling the water content is not particularly limited, and a known method can be used. For example, a method for producing a photosensitive coloring composition while blowing in a dry inert gas, or a method for dehydrating the composition by adding molecular sieves after production, etc. can be mentioned. Among them, the method for producing the composition while blowing in a dry inert gas is preferred.

[0135] The water content can be measured by a known method such as the Karl Fischer method.

[0136] <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. The preferred color filter according to this embodiment includes the above-mentioned green filter segment, red filter segment, and blue filter segment. The color filter segments other than those according to the present invention may be formed using a known coloring composition that contains a color pigment, a color dye, or both a color pigment and a color dye. The method for forming the color filter segment is not particularly limited, but it is common to use a photosensitive coloring composition that is a negative resist.

[0137] <Manufacturing method for color filters> It is preferable to form a color filter by first forming a black matrix on a substrate and then forming filter segments. It is also possible to form a thin film transistor (TFT) on the substrate before forming the black matrix. Examples of the black matrix include a multilayer film of chromium or chromium / chromium oxide, an inorganic film such as titanium nitride, and a resin film with a light-shielding agent dispersed therein.

[0138] The color filter of the present invention can be used for applications such as liquid crystal displays, organic EL displays, quantum dot displays, electronic paper, and head-mounted displays, in addition to solid-state imaging devices.

[0139] <Solid-state imaging element> The solid-state imaging device of the present invention includes the color filter of the present invention. The configuration of the solid-state imaging device of the present invention is not particularly limited as long as it is a configuration including the color filter for the solid-state imaging device of the present invention and functions as a solid-state imaging device, and examples thereof include the following configurations. The solid-state imaging device has a substrate on which are disposed a plurality of photodiodes constituting the light receiving area of ​​the solid-state imaging element (CCD sensor, CMOS sensor, organic CMOS sensor, etc.) and a transfer electrode made of polysilicon or the like, a light-shielding film made of tungsten or the like with only the light receiving portion of the photodiode being opened on the photodiodes and the transfer electrode, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire light-shielding film and the light receiving portion of the photodiode, and a color filter for the solid-state imaging element of the present invention on the device protection film. Furthermore, the device may have a light collecting means (such as a microlens, hereinafter the same) on the device protection layer and below the color filter (on the side closer to the substrate), or the light collecting means may be on the color filter. The organic CMOS sensor is composed of a thin panchromatic organic photoelectric conversion film as a photoelectric conversion layer and a CMOS signal readout substrate, and has a two-layer hybrid structure in which the organic material is responsible for capturing light and converting it into an electrical signal, and the inorganic material is responsible for extracting the electrical signal to the outside, and in principle, the aperture ratio for incident light can be 100%. The organic photoelectric conversion film is a structure-free continuous film that can be laid on the CMOS signal readout substrate, so it does not require expensive microfabrication processes and is suitable for miniaturizing filter segments. The arrangement of the color filter segments is not particularly limited, and any known method can be used. The color filter segment according to the present invention can be formed by any known method without any particular limitation, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, etc., but since the filter segments of a solid-state imaging element are minute, ranging from submicrons to about 10-odd microns, it is preferable to use photolithography. An embodiment of the present invention is a method for producing a color filter, characterized in that it has a color filter segment obtained by curing the above-mentioned coloring composition. The color filter includes a color filter segment obtained by curing the coloring composition according to the embodiment of the present invention described above. The color filter segment is formed by, for example, applying a photosensitive coloring composition containing a colorant of a certain color tone onto a transparent substrate so that the dry film thickness is about 0.1 to 5 μm. Examples of the coating device include spray coating, spin coating, slit coating, and roll coating. A drying step can be carried out during coating. Examples of the drying device include a hot air oven and an infrared heater. When color filter segments are formed by photolithography on corresponding photoelectric conversion elements, a negative color resist layer (hereinafter referred to as the first coating) is formed from a negative green film made of a negative photosensitive green composition, and the thickness of the negative color resist layer in this case is set in the range of 0.1 μm to 3.0 μm. The surface of the negative color resist layer formed of the negative color film is pattern-exposed using a photomask at a plurality of portions corresponding to a plurality of photoelectric conversion elements to be formed. The photomask has dimensions 4 to 5 times the dimensions of the pattern to be actually formed, and is reduced to 1 / 4 to 1 / 5 during pattern exposure. This photomask is a 4-5x reticle, and has a pattern that is 4-5x larger than the size of the pattern to be exposed on the surface of the negative color resist layer.Then, using a stepper exposure device, the photomask pattern is reduced to 1 / 4-1 / 5 and exposed on the surface of the negative color resist layer. In addition, a second coating (oxygen barrier film) can be formed on the first coating before exposure using polyvinyl alcohol or a water-soluble acrylic resin. This prevents the first coating from coming into contact with oxygen, further improving the exposure sensitivity. In addition, the color filter can be heated to cure the uncured photopolymerizable compound in the filter segment. Following the exposure step, an alkali development process (development step) is carried out to dissolve the uncured parts after exposure into a developer, leaving the photocured parts. This development step allows the formation of a patterned film made of color filter segments. The development method may be any of a dip method, a shower method, a spray method, a paddle method, etc., and these may be combined with a swing method, a spin method, an ultrasonic method, etc. It is also possible to prevent uneven development by pre-wetting the surface to be developed with water or the like before contacting the developing solution. As the developing solution, an organic alkaline developing solution that does not cause damage to the underlying circuitry is preferable. The developing temperature is usually 20°C to 30°C, and the developing time is 20 to 90 seconds. Examples of the alkaline agent contained in the developer include organic alkaline compounds such as ammonia water, ethylamine, diethylamine, dimethylethanolamine, dimethylbenzylamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene, and inorganic compounds such as sodium hydroxide, potassium hydroxide, sodium hydrogen carbonate, potassium hydrogen carbonate, and sodium carbonate. In addition, a defoaming agent or a surfactant can be added to the developer. As the developer, an alkaline aqueous solution obtained by diluting these alkaline agents with pure water to a concentration of 0.001% by mass to 10% by mass, preferably 0.01% by mass to 1% by mass, is preferably used. When a developer made of such an alkaline aqueous solution is used, after development, the excess developer is generally removed by washing (rinsing) with pure water, and then dried. Finally, the filter segment thus formed is subjected to a hardening treatment. In the manufacturing method of the present invention, after carrying out the above-mentioned colored layer forming step, exposure step, and development step, a curing step of curing the formed colored pattern by post-heating (post-baking) or post-exposure may be included as necessary. Post-baking is a heat treatment after development to complete the curing, and is usually a thermal curing treatment at 100°C to 270°C. When light is used, it can be performed by g-rays, h-rays, i-rays, excimer lasers such as KrF and ArF, electron beams, X-rays, etc., but it is preferable to perform it at a low temperature of about 20 to 50°C using an existing high-pressure mercury lamp, and the irradiation time is 10 seconds to 180 seconds, preferably 30 seconds to 60 seconds. When post-exposure and post-baking are used in combination, it is preferable to perform post-exposure first. The color filter having the desired hues is produced by repeating the color layer forming step, the exposure step, and the development step (and further, the curing step, if necessary) as many times as desired hues.

[0140] When the filter segments are formed by the printing method, the pattern can be formed by simply repeating printing and drying of the photosensitive coloring composition prepared as a printing ink, and therefore the method is low-cost and excellent in mass productivity as a 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 perform printing, 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.

[0141] When the filter segments are formed by the electrodeposition method, a transparent conductive film is formed on a transparent substrate, and the filter segments of each color are electrodeposited on the transparent conductive film by electrophoresis of colloidal particles to produce a color filter. In the transfer method, the filter segments are formed on the release-treated surface of a release sheet. The filter segments are then transferred to a transparent substrate to produce the color filter. EXAMPLES

[0142] The present invention will be described below with reference to examples. In the examples, "parts" and "%" represent "parts by mass" and "% by mass", respectively. It should be noted that Example 148 is a reference example.

[0143] Prior to the examples, the methods for measuring and calculating the average molecular weight of a resin and the acid value of a resin will be described.

[0144] (Average molecular weight of binder resin) The mass average molecular weight (Mw) of the resin was 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 flow rate was 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent, and 20 microliters were injected. All molecular weights are polystyrene equivalent values.

[0145] (Average molecular weight of resin-type dispersant) The weight average molecular weight (Mw) of the resin-type dispersant is the polystyrene-equivalent number average molecular weight (Mn) and weight average molecular weight (Mw) measured using an HLC-8320GPC (manufactured by Tosoh Corporation) as the apparatus, a SUPER-AW3000 as the column, and an N,N-dimethylformamide solution of 30 mM triethylamine and 10 mM LiBr as the eluent.

[0146] (Acid value of resin) 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.

[0147] (Amine value of basic resin type dispersant (mgKOH / g)) The amine value of the basic resin-type dispersant is the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 and converted into non-volatile content.

[0148] (Volume average primary particle size of pigment) The volume average primary particle size (MV) of a pigment was determined by measuring the short and long axis diameters of 100 primary particles of the pigment using transmission electron microscope (TEM) photographs, taking the average of the short and long axis diameters as the particle size (d) of the pigment particle, and then determining the volume (V) of each particle by assuming that each pigment is a sphere having the determined particle size. This procedure was performed for 100 pigment particles, and then calculated from the following formula. MV = Σ(V d) / Σ(V)

[0149] (Number of halogen substitutions in pigment) The number of halogen substitutions in the pigment was obtained by burning the pigment by an oxygen combustion flask method, absorbing the combustion product in water, analyzing the liquid by ion chromatography (ICS-2000 ion chromatography, manufactured by DIONEX Corporation), quantifying the amount of halogen, and converting it into the number of halogen substitutions.

[0150] (Halogen distribution width in pigment) The halogen distribution width in the pigment was determined using a time-of-flight mass spectrometer (AutofleXIII (TOF-MS), Bruker Daltonics). The halogen content was determined by calculating the signal intensity (each peak value) of the molecular ion peak corresponding to each component in the mass spectrum obtained by mass spectrometry of the pigment powder and the integrated value of each peak value (total peak value), and then calculating the ratio of each peak value to the total peak value. The halogen distribution width was determined by counting the number of peaks whose ratio of each peak value to the total peak value was 1% or more.

[0151] <Method for producing a solution of basic resin-type dispersant (B1)> (Basic resin type dispersant solution (B1-1) A reaction apparatus equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 4.0 parts of AIBN (2,2'-azobisisobutyronitrile) and 133 parts of PGMAc, followed by 7.8 parts of ethyl acrylate, 39.0 parts of methyl methacrylate, 31.2 parts of n-butyl methacrylate, and 5.0 parts of 2,2,6,6-tetramethyl-1-piperidinyloxy radical (TEMPO), and substituted with nitrogen for 30 minutes. After that, the reaction solution was gently stirred to raise the temperature to 80°C, and this temperature was maintained for 12 hours to carry out living radical polymerization. Next, 22.0 parts of N,N-dimethylaminoethyl methacrylate was dissolved in this reaction solution, and the mixture was substituted with nitrogen for 30 minutes, and living radical polymerization was carried out at 80 ° C for 12 hours. After cooling to room temperature, the mixture was concentrated to 60% by weight or more using an evaporator, and about 2 g of the resin solution was sampled and dried by heating at 180 ° C for 20 minutes to measure the non-volatile content. PGMAc was added to the previously synthesized dispersant so that the non-volatile content was 50% by weight, and a basic resin-type dispersant solution (B1-1) was prepared. As a result of GPC measurement, the weight average molecular weight (Mw) was 8100. In addition, the amine value per solid content was 79.0 mg KOH / g.

[0152] (Basic resin type dispersant solution (B1-2 to B1-4)) Except for changing the composition shown in Table 1, basic resin type dispersant solutions (B1-2 to 4) were obtained in the same manner as for the basic resin type dispersant solution (B1-1).

[0153] [Table 1]

[0154] <Method for producing acidic resin-type dispersant (B2) solution> (Production Example 1) (Acidic Resin-Type Dispersant Solution (B2-1)) In a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 parts of monobutyltin (IV) oxide as a catalyst were charged, and the mixture was replaced with nitrogen gas, and then heated and stirred at 120 ° C for 4 hours. After confirming that 98% had reacted by measuring the non-volatile content, 73.3 parts of pyromellitic anhydride were added and reacted at 120 ° C for 2 hours. The reaction was terminated when it was confirmed that 98% or more of the acid anhydride had been half-esterified by measuring the acid value. The obtained dispersant was a white solid at room temperature and had an acid value of 49 mg KOH / g. The solution was concentrated to 60% by weight or more using an evaporator, and the non-volatile content was adjusted with propylene glycol monomethyl ether acetate (hereinafter sometimes abbreviated as PGMAc) to obtain an acidic resin-type dispersant solution (B2-1) with a non-volatile content of 50%.

[0155] (Production Example 2) (Acidic Resin-Type Dispersant Solution (B2-2)) A reaction vessel equipped with a gas inlet tube, temperature control, condenser, and stirrer was charged with 20 parts of methyl methacrylate, 140 parts of 2-methoxyethyl methacrylate, 40 parts of n-butyl acrylate, and 50 parts of PGMAc, and the atmosphere was replaced with nitrogen gas. The inside of the reaction vessel was heated to 50°C with stirring, 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 in 90 parts of PGMAc was added and reacted for 7 hours. Measurement of the non-volatile content confirmed that 95% had reacted. 35 parts of trimellitic anhydride, 370 parts of PGMAc, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted for 7 hours at 100° C. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and the mixture was concentrated to 60% by weight or more using an evaporator. PGMAc was added to dilute the mixture so that the non-volatile content was 50% by measuring the non-volatile content, and an acidic resin-type dispersant solution (B2-2) with an acid value of 40 mgKOH / g and a weight average molecular weight of 9000 was obtained.

[0156] (Production Examples 3 to 9) (Acidic Resin-Type Dispersant Solutions (B2-3 to 9)) Synthesis was carried out in the same manner as in Production Example 2, except that the raw materials and the amounts charged were used as shown in Table 2, to obtain resin-type dispersant solutions (B2-3 to B2-9).

[0157] [Table 2]

[0158] <Method for producing colorant (A)> <Method for producing phthalocyanine pigment (A1)> (Micronized pigment (P-1)) In a three-neck flask, 500 parts of 98% sulfuric acid, 50 parts of the phthalocyanine pigment (P-11) represented by formula (50), and 129.3 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred, and reacted at 20°C for 6 hours. Then, the above reaction mixture was poured into 5,000 parts of ice water at 3°C, and the precipitated solid was filtered and washed with water. 500 parts of a 2.5% aqueous sodium hydroxide solution and the filtered residue were added to a beaker, and the mixture was stirred at 80°C for 1 hour. Then, the mixture was filtered, washed with water, and dried to obtain a pigment in which an average of 10.1 bromine atoms were substituted on the phthalocyanine ring. Next, 500 parts of N-methylpyrrolidone, 50 parts of the pigment having an average of 10.1 bromine atoms substituted on the phthalocyanine ring, and 13.9 parts of diphenyl phosphate were added to a three-neck flask, heated to 90°C, and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain the phthalocyanine pigment (P-1) represented by the following formula (51). The pigment had a halogen distribution width of 9 and a volume average primary particle diameter of 26 nm.

[0159] [ka]

[0160] (Micronized pigment (P-2)) In a three-neck flask, 500 parts of 98% sulfuric acid, 50 parts of the phthalocyanine pigment represented by the above formula (50), and 104.4 parts of 1,2-dibromo-5,5-dimethylhydantoin (DBDMH) were added and stirred, and reacted at 20°C for 4 hours. Then, the above reaction mixture was poured into 5,000 parts of ice water at 3°C, and the precipitated solid was filtered and washed with water. 500 parts of 2.5% aqueous sodium hydroxide solution and the filtered residue were added to a beaker, and stirred at 80°C for 1 hour. Then, this mixture was filtered, washed with water, and dried to obtain a pigment in which an average of 8.0 bromine atoms were substituted on the phthalocyanine ring. Next, 500 parts of N-methylpyrrolidone, 50 parts of the pigment having an average of 8.0 bromine atoms substituted on the phthalocyanine ring, and 15.8 parts of diphenyl phosphate were added to a three-neck flask, heated to 90°C, and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain the phthalocyanine pigment (P-2) represented by the following formula (52). The halogen distribution width was 9. The volume average primary particle diameter of the pigment was 33 nm.

[0161] Formula (52) [ka]

[0162] (Micronized pigment (P-3)) 203 parts of aluminum bromide, 47 parts of sodium bromide, and 5 parts of ferric bromide were heated to melt, and 50 parts of the phthalocyanine pigment represented by formula (50) were added at 140°C. The mixture was heated to 160°C, and reacted at 160°C for 7 hours while blowing in 215.4 parts of bromine. The above reaction mixture was poured into 2500 parts of ice water at 3°C, and the precipitated solid was filtered and washed with water. The residue was washed with 1% aqueous hydrochloric acid, warm water, 1% aqueous sodium hydroxide solution, and warm water in this order, and then dried to obtain 98 parts of brominated aluminum phthalocyanine. The obtained crude brominated aluminum phthalocyanine was dissolved in 980 parts of concentrated sulfuric acid, and stirred at 50°C for 3 hours. Then, the above sulfuric acid solution was poured into 9800 parts of ice water at 3°C, and the precipitated solid was filtered, washed with water, and dried. Next, 500 parts of 2.5% aqueous sodium hydroxide solution and the filtered residue were added to a beaker, and stirred at 80°C for 1 hour. Thereafter, the mixture was filtered, washed with water, and dried to obtain a pigment having an average of 15.0 bromine atoms substituted on the phthalocyanine ring. Next, 500 parts of N-methylpyrrolidone, 50 parts of the pigment having an average of 15.0 bromine atoms substituted on the phthalocyanine ring, and 10.8 parts of diphenyl phosphate were added to a three-neck flask, heated to 90°C, and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain the phthalocyanine pigment (P-3) represented by the following formula (53). The halogen distribution width was 4. The volume average primary particle diameter of the pigment was 40 nm.

[0163] Formula (53) [ka]

[0164] (Micronized pigment (P-4)) In a three-neck flask, 500 parts of N-methylpyrrolidone, 50 parts of the pigment prepared in (P-2) in which an average of 8.0 bromine atoms are substituted on the phthalocyanine ring, and 13.8 parts of diphenylphosphinic acid were added, heated to 90°C, and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain the phthalocyanine pigment (P-4) represented by the following formula (54). The halogen distribution width was 9. The volume average primary particle diameter of the pigment was 45 nm.

[0165] Formula (54) [ka]

[0166] (Micronized pigment (P-5)) In a reaction vessel, 225 parts of phthalodinitrile and 78 parts of aluminum chloride anhydride were added to 1250 parts of n-amyl alcohol and stirred. 266 parts of DBU (1,8-Diazabicyclo[5.4.0]undec-7-ene) were added to the mixture, and the mixture was heated and refluxed at 136°C for 5 hours. The reaction solution was cooled to 30°C while stirring, and poured into a mixed solvent of 5000 parts of methanol and 10000 parts of water under stirring to obtain a blue slurry. The slurry was filtered, washed with a mixed solvent of 2000 parts of methanol and 4000 parts of water, and dried to obtain 135 parts of chloroaluminum phthalocyanine. Furthermore, 100 parts of chloroaluminum phthalocyanine were slowly added to 1200 parts of concentrated sulfuric acid in a reaction vessel at room temperature. The mixture was stirred at 40°C for 3 hours, and the sulfuric acid solution was poured into 24000 parts of cold water at 3°C. The blue precipitate was filtered, washed with water, and dried to obtain 102 parts of a phthalocyanine pigment (P-10) represented by the following formula (55).

[0167] Formula (55) [ka]

[0168] Next, 250 parts of aluminum chloride, 60 parts of sodium chloride, and 2.25 parts of iodine were added to a three-necked flask and stirred at 150°C for 30 minutes. 50 parts of aluminum phthalocyanine pigment represented by formula (55) was added thereto and stirred at 155°C for 30 minutes to dissolve. 58.5 parts of trichloroisocyanuric acid was further added and stirred at 190°C for 5 hours. Then, the above reaction mixture was poured into 5,000 parts of ice water at 3°C, and the precipitated solid was filtered and washed with water. 500 parts of 2.5% aqueous sodium hydroxide solution and the filtered residue were added to a beaker and stirred at 80°C for 1 hour. Then, the mixture was filtered, washed with water, and dried to obtain a pigment in which an average of 8.1 chlorine atoms were substituted on the phthalocyanine ring. Next, 500 parts of N-methylpyrrolidone, 50 parts of the pigment having an average of 8.1 bromine atoms substituted on the phthalocyanine ring, and 22.6 parts of diphenyl phosphate were added to a three-neck flask, heated to 90°C, and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain the phthalocyanine pigment (P-5) represented by the following formula (56). The halogen distribution width was 8. The volume average primary particle diameter of the pigment was 36 nm.

[0169] Formula (56) [ka]

[0170] (Micronized pigment (P-6)) In a reaction vessel, 100 parts of the phthalocyanine pigment represented by formula (55) and 49.5 parts of diphenyl phosphate were added to 1,000 parts of methanol, heated to 40° C., and reacted for 8 hours. After cooling to room temperature, the product was filtered, washed with methanol, and dried to obtain 114 parts of the phthalocyanine pigment represented by the following formula (57).

[0171] Formula (57) [ka]

[0172] Next, 100 parts of the mixture, 1200 parts of sodium chloride, and 120 parts of diethylene glycol 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, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. overnight to obtain a fine pigment (P-6). The volume average primary particle diameter of the pigment was 37 nm.

[0173] (Micronized pigment (P-7)) In the synthesis of the phthalocyanine pigment of formula (57), except that 43.2 parts of diphenylphosphinic acid was used instead of diphenyl phosphate, the phthalocyanine pigment described in formula (58) was obtained in the same manner. Then, the phthalocyanine pigment (P-7) was produced by carrying out a micronization treatment in the same manner as (P-6). The volume average primary particle diameter of the pigment was 29 nm.

[0174] Formula (58) [ka]

[0175] (Micronized pigment (P-8)) In the synthesis of the phthalocyanine pigment of formula (57), except that 250 parts of 4-methylphthalodinitrile was used instead of phthalodinitrile and 28.0 parts of phenylphosphinic acid was used instead of diphenyl phosphate, the phthalocyanine pigment described in formula (59) was obtained in the same manner. Then, the same micronization treatment as in (P-6) was carried out to produce the phthalocyanine pigment (P-8). The volume average primary particle diameter of the pigment was 33 nm.

[0176] Formula (59) [ka]

[0177] (Phthalocyanine pigment (P-11)) Commercially available CI Pigment Green 58 (FASTOGEN Green A110 manufactured by DIC) was used as is. Fluorescent X-ray analysis revealed that the average number of halogen atoms per molecule was 15.46, of which the average number of bromine atoms was 14.75 and the average number of chlorine atoms was 0.71. The average primary particle diameter was 19 nm.

[0178] (Phthalocyanine pigment (P-12)) 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 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, 2 parts of resin-type dispersant (B2-3) solution, 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 halogenated zinc phthalocyanine pigment. The obtained halogenated zinc phthalocyanine pigment was found to have an average of 8.88 halogen atoms per molecule from fluorescent X-ray analysis, of which the average number of bromine atoms was 6.90 and the average number of chlorine atoms was 1.98, making it a phthalocyanine pigment. The average primary particle size was 15 nm.

[0179] (Phthalocyanine pigment (P-13)) 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 halogenated zinc phthalocyanine pigment. The obtained halogenated zinc phthalocyanine pigment 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. The average primary particle size was 18 nm.

[0180] (Micronized pigment (P-14)) 500 parts of phthalocyanine green pigment CI Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyo Color Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 4 hours at 120°C. Next, this kneaded material was put into 5 liters of warm water, heated to 70°C and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for a day and night to obtain 490 parts of finely divided pigment (P-14). The average primary particle size was 22 nm.

[0181] <Method for producing quinophthalone pigment (A2)> (Micronized pigment (P-15)) 100 parts of CI Pigment Yellow 138 (PY138) (BASF Japan "Paliotol Yellow K0960-HD"), 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho) and kneaded for 6 hours at 80°C. This mixture was added to 2000 parts of warm water and stirred for 1 hour while heating to 80°C to form a slurry. After repeatedly filtering and washing with water to remove salt and solvent, the mixture was dried at 80°C for a day and night to obtain a fine pigment (P-15). The average primary particle size was 24 nm.

[0182] (Micronized pigment (P-16)) Compound (1) was obtained according to the synthesis method described in JP 2008-81566 A.

[0183] Compound (1) [ka]

[0184] 100 parts of compound (1), 108 parts of tetrachlorophthalic anhydride, and 143 parts of benzoic acid were added to 300 parts of methyl benzoate, and the mixture was heated to 180° C. and reacted for 4 hours. The production of quinophthalone compound (a) and the disappearance of the raw material compound (1) were confirmed by TOF-MS.

[0185] Quinophthalone Compound (a) [ka]

[0186] After cooling to room temperature, the reaction mixture was poured into 3510 parts of acetone and stirred at room temperature for 1 hour. The product was separated by filtration, washed with methanol, and dried to obtain 120 parts of quinophthalone compound (a).

[0187] Next, 100 parts of the obtained quinophthalone compound (a), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 8 hours at 60° C. Next, this kneaded product was put into warm water, heated to about 70° C. and stirred for 1 hour to form a slurry, which was then filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. for one day to obtain 98 parts of a finely divided pigment (P-16). The average primary particle diameter was 31 nm.

[0188] <Method of manufacturing metal azo pigment (A3)> The azobarbituric acid precursor was prepared according to the synthesis method described in JP 2017-171915 A. (Instruction 1) 46.2 g of diazobarbituric acid and 38.4 g of barbituric acid were introduced into 1100 g of distilled water at 85° C. The pH was then adjusted to about pH 5 with an aqueous potassium hydroxide solution and stirring was continued for 90 minutes.

[0189] (Micronized pigment (P-17)) The azobarbituric acid (0.3 mol) prepared in instruction 1 was mixed with 1500 g of distilled water at 82°C. 75.7 g of melamine (0.6 mol) were then introduced. 0.3 mol of about 30% strength zinc chloride solution was then added dropwise. After 3 hours at 82°C, the pH was adjusted to about 5.5 with KOH. This was followed by dilution with about 300 g of distilled water at 90°C. 34 g of 30% strength hydrochloric acid were then added dropwise and the temperature was kept at 90°C for 12 hours. The pH was then adjusted to about 5 with aqueous potassium hydroxide solution. The pigment was then isolated on a suction filter, washed, dried at 80°C in a vacuum drying cabinet and ground in a standard laboratory mill for 2 minutes. (adduct of zinc azobarbituric acid with melamine) Then, 100 parts of the prepared pigment, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 6 hours (kneading process). This kneaded mixture was added to 3000 parts of warm water, heated to 70°C and stirred for 1 hour to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for one day to obtain 97 parts of a finely divided pigment (P-17). The volume average primary particle diameter of the pigment was 37 nm.

[0190] (Micronized pigment (P-18)) Azobarbituric acid (0.3 mol) prepared in instruction 1 was mixed with 1500 g of distilled water at 82 ° C. Then 10 g of 30% strength hydrochloric acid was added dropwise to adjust the pH to 2-2.5. After that, 79.4 g of melamine (0.63 mol) was introduced. Then 0.3 mol of about 25% strength nickel chloride solution was added dropwise. After 3 hours at 82 ° C, the pH was adjusted to about 5.5 with KOH. This was followed by dilution with about 100 g of distilled water at 90 ° C. Then 21 g of 30% strength hydrochloric acid was added dropwise and the temperature was kept at 90 ° C for 12 hours. After that, the pH was adjusted to about 5 with aqueous potassium hydroxide solution. The pigment was then isolated on a suction filter, washed, dried at 80 ° C in a vacuum drying cabinet and ground in a standard laboratory mill for 2 minutes. (Adduct of nickel azobarbituric acid and melamine) Thereafter, a kneading process was carried out in the same manner as in (P-16), to obtain 97 parts of a finely divided pigment (P-18). The volume average primary particle diameter of the pigment was 29 nm.

[0191] (Micronized pigment (P-19)) The micronized pigment (P-19) was obtained in the same manner as the micronized pigment (P-18), except that the "0.3 moles of 25% strength nickel chloride solution" in the preparation example for the micronized pigment (P-18) was replaced by a "mixed solution of 0.225 moles of 25% strength nickel chloride + 0.075 moles of 25% strength zinc chloride". (Melamine adduct of zinc / nickel azobarbituric acid, a hybrid compound with the components 25 mole % Zn and 75 mole % nickel) The volume average primary particle size of the pigment was 37 nm.

[0192] (Micronized pigment (P-20)) The micronized pigment (P-20) was obtained in the same manner as the micronized pigment (P-18), except that the "0.3 moles of 25% strength nickel chloride solution" in the preparation example for the micronized pigment (P-18) was replaced by "0.150 moles of a mixed solution of 25% strength nickel chloride + 0.150 moles of 25% strength zinc chloride". (Melamine adduct of zinc / nickel azobarbituric acid, a hybrid compound with 50 mole % Zn and 50 mole % nickel components) The volume average primary particle size of the pigment was 25 nm.

[0193] (Micronized pigment (P-21)) The micronized pigment (P-21) was obtained in the same manner as the micronized pigment (P-18), except that the "0.3 moles of 25% strength nickel chloride solution" in the preparation example for the micronized pigment (P-18) was replaced by a "mixed solution of 0.075 moles of 25% strength nickel chloride + 0.225 moles of 25% strength zinc chloride". (Melamine adduct of zinc / nickel azobarbituric acid, a hybrid compound with 75 mole % Zn and 25 mole % nickel components) The volume average primary particle size of the pigment was 23 nm.

[0194] <Method of producing dye derivative> (Dye derivative (DE-1)) A dye derivative (DE-1) was obtained according to the synthesis method described in JP 2011-39307 A.

[0195] Dye derivative (DE-1) [ka]

[0196] Dye derivative (DE-2) A dye derivative (DE-2) was obtained according to the synthesis method described in JP 2018-17856 A.

[0197] Dye derivative (DE-2) [ka]

[0198] Dye derivative (DE-3) A dye derivative (DE-3) was obtained according to the synthesis method described in JP-A-2007-156395.

[0199] [ka]

[0200] <Method for producing binder resin (E)> (Preparation of binder resin (E-1) solution) 89 parts of PGMAc was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable 4-neck flask, and heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 7.0 parts of styrene, 32.2 parts of glycidyl methacrylate, 27.7 parts of dicyclopentanyl methacrylate, and 4.0 parts of azobisisobutyronitrile was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 16.3 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added, and the reaction was continued at 120°C for 5 hours. When the acid value of the solid content reached 0.8, the reaction was terminated to obtain a resin solution. Further, 16.8 parts of succinic anhydride and 0.5 parts of triethylamine were added and reacted at 120°C for 4 hours, and PGMAc was added so that the non-volatile content was 50% to prepare a binder resin (E-1) solution. The weight average molecular weight (Mw) was 5100 and the acid value was 98 mgKOH / g.

[0201] (Preparation of binder resin (E-2) solution) 89 parts of PGMAc was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable 4-neck flask, and heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 3.9 parts of styrene, 32.3 parts of glycidyl methacrylate, 25.0 parts of dicyclopentanyl methacrylate, and 3.2 parts of azobisisobutyronitrile was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 16.3 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added, and the reaction was continued at 120°C for 5 hours. When the acid value of the solid content reached 0.8, the reaction was terminated to obtain a resin solution. Further, 22.5 parts of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added and reacted at 120°C for 4 hours, and PGMAc was added so that the non-volatile content became 50% to prepare a binder resin (E-2) solution. The weight average molecular weight (Mw) was 9000 and the acid value was 80 mgKOH / g.

[0202] (Preparation of binder resin (E-3) solution) 182 parts of PGMAc was placed in a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer as a reaction vessel, and the vessel was heated to 100°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 57.6 parts of benzyl methacrylate, 12.9 parts of dicyclopentanyl methacrylate, 17.0 parts of methacrylic acid, 98 parts of PGMAc, and 3.6 parts of azobisisobutyronitrile was added dropwise from the dropping tube over 2 hours, and the mixture was further stirred at 100°C for 5 hours to carry out a polymerization reaction. Next, the inside of the flask was replaced with air, and 12.5 parts of glycidyl methacrylate, 0.9 parts of trisdimethylaminomethylphenol, and 0.145 parts of hydroquinone were added, and the reaction was continued for 6 hours at 110°C. When the acid value of the solid content reached 0.8, the reaction was continued, and PGMAc was added so that the non-volatile content became 50%, and a binder resin (E-3) solution with a weight average molecular weight (Mw) of 9200 and an acid value of 65 mgKOH / g was obtained.

[0203] (Preparation of binder resin (E-4) solution) 182 parts of PGMAc was placed in a separable 4-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer as a reaction vessel, and the vessel was heated to 100°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 9.8 parts of benzyl methacrylate, 6.3 parts of dicyclopentanyl methacrylate, 41.6 parts of methacrylic acid, 98 parts of PGMAc, and 4.0 parts of azobisisobutyronitrile was added dropwise from the dropping tube over 2 hours, and the mixture was further stirred at 100°C for 5 hours to carry out a polymerization reaction. Next, the inside of the flask was replaced with air, and 42.3 parts of glycidyl methacrylate, 0.9 parts of trisdimethylaminomethylphenol, and 0.145 parts of hydroquinone were added, and the reaction was continued for 6 hours at 110°C. When the acid value of the solid content reached 0.8, the reaction was continued, and PGMAc was added so that the non-volatile content was 50%, and a binder resin (E-4) solution with a weight average molecular weight (Mw) of 6500 and an acid value of 160 mgKOH / g was obtained.

[0204] (Preparation of binder resin (E-5) solution) 89 parts of PGMAc was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable 4-neck flask, and heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 14.2 parts of styrene, 26.0 parts of glycidyl methacrylate, 30.1 parts of dicyclopentanyl methacrylate, and 2.4 parts of azobisisobutyronitrile was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 13.2 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added, and the reaction was continued at 120°C for 5 hours. When the acid value of the solid content reached 0.8, the reaction was terminated to obtain a resin solution. Further, 16.7 parts of trimellitic anhydride and 0.5 parts of triethylamine were added and reacted at 120°C for 4 hours, and PGMAc was added so that the non-volatile content became 50% to prepare a binder resin (E-5) solution. The weight average molecular weight (Mw) was 11,000 and the acid value was 90 mgKOH / g.

[0205] (Preparation of binder resin (E-6) solution) 89 parts of PGMAc was placed in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer in a separable 4-neck flask, and heated to 120°C while injecting nitrogen gas into the vessel. At the same temperature, a mixture of 7.0 parts of styrene, 32.2 parts of glycidyl methacrylate, 27.7 parts of dicyclopentanyl methacrylate, and 1.0 part of azobisisobutyronitrile was added dropwise from the dropping tube over 2.5 hours to carry out a polymerization reaction. Next, the atmosphere in the flask was replaced with air, and 16.3 parts of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added, and the reaction was continued at 120°C for 5 hours. When the acid value of the solid content reached 0.8, the reaction was terminated to obtain a resin solution. Further, 16.8 parts of succinic anhydride and 0.5 parts of triethylamine were added and reacted at 120°C for 4 hours, and PGMAc was added so that the non-volatile content was 50% to prepare a binder resin (E-6) solution. The weight average molecular weight (Mw) was 16,000 and the acid value was 95 mgKOH / g.

[0206] <Production of colored composition using colorant (A)> [Preparation Example 1] (Preparation of Colored Composition (G-1) Using Colorant (A)) The mixture below was stirred and mixed until homogeneous, and then dispersed for 5 hours in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm. The mixture was then filtered through a 5.0 μm filter to obtain a colored composition (G-1). The colored composition was adjusted with PGMAc to have a non-volatile content of 20% by mass. Fine pigment (P-1): 15.0 parts Basic resin type dispersant solution (B1-1): 5.5 parts Acidic resin type dispersant solution (B2-3): 4.5 parts PGMAc: 75.0 copies

[0207] [Examples 2-115] (Preparation of colored compositions (G-2 to 115) using colorant (A)) Except for changing the compositions shown in Tables 3, 4 and 5, colored compositions (G-2 to 115) were obtained in the same manner as for colored composition (G-1).

[0208] [Table 3]

[0209] [Table 4]

[0210] [Table 5]

[0211] <Production of Photosensitive Coloring Composition> [Example 1] (Preparation of Photosensitive Coloring Composition (R-1)) The mixture having the following composition was stirred and mixed uniformly, and then filtered through a 1 μm filter to prepare a photosensitive coloring composition (R-1). Coloring composition (G-9): 55.2 parts Coloring composition (G-31): 19.7 parts Coloring composition (G-69): 6.9 parts Binder resin solution (E-1): 2.3 parts Polymerizable compound (Aronix M-402: manufactured by Toagosei Co., Ltd.): 2.2 parts Photopolymerization initiator (D-1): 0.24 parts Polymerization inhibitor solution (methylhydroquinone): 3.6 parts (Solution adjusted with PGMAc to a non-volatile content of 1% by mass) PGMAc: 5.86 parts Leveling agent solution: 4.0 parts (Toray Dow Corning "FZ-2122" (Solution adjusted with PGMAc to a non-volatile content of 1% by mass)

[0212] [Examples 2 to 153, Comparative Examples 1 to 3] (Preparation of Photosensitive Coloring Compositions (R-2 to 156)) Photosensitive coloring compositions (R-2 to R-156) were obtained in the same manner as the photosensitive coloring composition (R-1), except that the materials and blending amounts used in the photosensitive coloring composition (R-1) were changed as shown in Tables 6-1 to 4. However, the blending amounts of the polymerization inhibitor solution and the leveling agent solution were the same as in Example 1.

[0213] [Table 6-1]

[0214] [Table 6-2]

[0215] [Table 6-3]

[0216] [Table 6-4]

[0217] The raw materials listed in Tables 6-1 to 6-4 are shown below. <Polymerizable compound> C-1 Aronix M-402 (manufactured by Toagosei Co., Ltd.: dipentaerythritol penta- and hexaacrylate) C-2 Aronix M-450 (manufactured by Toagosei Co., Ltd.: pentaerythritol tri- and tetraacrylate) C-3 KAYARAD DPEA-12 (manufactured by Nippon Kayaku: acrylate monomer with 5 or more functional groups) C-4 Urethane acrylate: Dipentaerythritol pentaacrylate hexamethylene diisocyanate (reaction product of dipentaerythritol pentaacrylate and hexamethylene diisocyanate) C-5 Aronix M-350 (Toagosei Co., Ltd.: Trimethylolpropane EO modified triacrylate)

[0218] <Photopolymerization initiator> D-1 OXE-04 (BASF Japan) D-2 OXE-02 (BASF Japan) D-3 TR-PBG-3057 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) D-4 TR-PBG-345 (manufactured by Changzhou Strong Electronic New Materials Co., Ltd.) D-5 Photopolymerization initiator C-4 described in JP 2018-116258 A D-6 Photopolymerization initiator C-5 described in JP 2018-116258 A D-7 Photopolymerization initiator C-6 described in JP 2018-116258 A D-8 Photopolymerization initiator C-7 described in JP 2018-116258 A

[0219] <Evaluation of Photosensitive Coloring Composition> The obtained photosensitive coloring compositions (R-1 to 156) were evaluated for light transmittance, residue, and adhesion by the following methods. The evaluation results are shown in Tables 7-1 to 7-4.

[0220] <Measurement of transmittance of photosensitive composition> The photosensitive coloring composition described in the Examples was applied to a glass substrate using a spin coater to form a coating film, which was then heated on a hot plate at 70° C. for 60 seconds to obtain a substrate with a film thickness of 0.7 μm. Next, the resulting coated substrate was exposed to i-line light (exposure dose 3000 J / m) through a mask having an island pattern of 500 μm square using an i-line exposure machine (ATS-4003 manufactured by Asahi Techno Solutions Corporation). 2). The exposed coating was then developed using a developing device (ADE-3000S manufactured by Actes). A 0.075% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used as the developer, and shower development was carried out at 23°C for 40 seconds. After that, rinsing was carried out with a spin shower using pure water, and then heating was carried out on a hot plate at 230°C for 20 minutes to obtain a patterned substrate. The light transmittance of the prepared substrate at wavelengths of 380 to 780 nm was measured using a microspectrophotometer (Lambda Vision's "LVmicro-Z"), and the light transmittance of the obtained pattern at a film thickness of 0.6 μm was calculated using a spreadsheet software (Lotus Software's "Lotus 1-2-3"), and the light transmittance of each wavelength was evaluated as follows. ◯ and △ are practical. Transmittance 1 (450 nm wavelength light transmittance evaluation) ○: Less than 9.0% △: 9.0% or more but less than 9.5% ×: 9.5% or more Transmittance 2 (evaluation of light transmittance at a wavelength of 525 nm) 〇: 94.5% or more △: 94.0% or more but less than 94.5% ×: Less than 94.0%

[0221] <Residue evaluation> Hexamethyldisilazane was applied to an 8-inch (200 mm) silicon wafer, heated on a hot plate at 100°C for 60 seconds, and then heated on a hot plate at 230°C for 180 seconds to produce a silicon wafer with a hydrophobic surface. The photosensitive coloring composition thus obtained was applied onto the prepared silicon wafer using a spin coater so that the film thickness after drying would be 0.8 μm, and heat treatment was carried out using a hot plate at 70° C. for 100 seconds. The resulting coating was then exposed to light with a wavelength of 365 nm (exposure dose 3000 J / m) through a mask having an island pattern of 1.2 μm square using an i-line stepper exposure system FPA-3000 i4 (Canon Corporation). 2). The exposed coating was then developed using a developing device (Act-8 manufactured by Tokyo Electron Ltd.). A 0.1% by mass aqueous solution of tetramethylammonium hydroxide (TMAH) was used as the developer, and shower development was carried out for 80 seconds at 23°C. Thereafter, rinsing was carried out with a spin shower using pure water to obtain a pattern. The obtained pattern was observed (magnification: 20,000 times) using a scanning electron microscope (SEM) (S-8820 manufactured by Hitachi High-Technologies Corporation) and the residue was evaluated. The evaluation criteria are as follows: ◯ and △ are practical. ◯: No residue in non-image areas between patterns △: Residue with a maximum length of less than 0.10 μm is observed in the non-image area between patterns. ×: Residues with a maximum length of 0.10 μm or more are observed in non-image areas between patterns.

[0222] <Adhesion> Among the patterns produced for residue evaluation, a group of patterns with a pattern size of 1.2 μm were observed with an optical microscope (Olympus Corporation) (magnification: 100 times). The evaluation criteria are as follows: ◯ and △ are practical. ○: No peeling or chipping of the pattern △: Pattern peeling and chipping is less than 10% in total ×: Pattern peeling and chipping is 10% or more in total

[0223] [Table 7-1]

[0224] [Table 7-2]

[0225] [Table 7-3]

[0226] [Table 7-4]

[0227] From the results in the above table, the photosensitive coloring compositions of Examples 1 to 153 showed excellent light transmittance, and the polymerizable compound having 4 or more ethylenically unsaturated double bonds was 1% by weight or more and 15% by weight or less in the total solid content of the photosensitive coloring composition, so the residue and adhesion were also good. On the other hand, Comparative Example 1 did not contain colorant (A2), and thus the light transmittance was poor. Comparative Example 2 did not contain colorant (A3), and thus the light transmittance was poor at a wavelength of 450 nm. Comparative Example 3 had a low concentration of colorant in the total solid content, and thus the light transmittance was poor at a wavelength of 450 nm.

[0228] <Manufacturing of color filters> Next, a photosensitive red coloring composition prepared in the same manner as in Example 1 was applied to a silicon wafer substrate using a spin coater, except that all of (G-31) and (G-69) in the coloring composition used in the photosensitive coloring composition (R-1) were replaced with (G-9), and the colorant in the replaced coloring composition (G-9) was replaced with CI Pigment Red 254, to form a colored coating. Next, the coating was irradiated with 3000 J / m 2 using an ultra-high pressure mercury lamp through a photomask. 2 Next, the unexposed areas were removed by spray development with an alkaline developer (aqueous solution of 0.1% by mass of tetramethylammonium hydroxide), and then the substrate was washed with ion-exchanged water and heated at 230° C. for 5 minutes to form red filter segments.

[0229] Similarly, a photosensitive blue coloring composition prepared in the same manner as in Example 1 was applied to a silicon wafer substrate by a spin coater, except that all of (G-31) and (G-69) in the coloring composition used in the photosensitive coloring composition (R-1) were replaced with (G-9), and the colorant in the replaced coloring composition (G-9) was replaced with CI Pigment Blue 15:6, to form a colored coating. Next, the coating was irradiated with 3000 J / m 2 using an ultra-high pressure mercury lamp through a photomask. 2Next, the unexposed areas were removed by spray development using an alkaline developer (aqueous solution of 0.1% by mass of tetramethylammonium hydroxide), and then the substrate was washed with ion-exchanged water and heated at 230° C. for 5 minutes to form blue filter segments, thereby obtaining a color filter.

[0230] Similarly, the photosensitive coloring composition (R-1) was applied to a silicon wafer substrate by a spin coater to form a colored film. Next, the film was irradiated with 3000 J / m 2 of an ultra-high pressure mercury lamp through a photomask. 2 The substrate was then spray-developed with an alkaline developer consisting of a 0.05% by mass aqueous solution of tetramethylammonium hydroxide to remove the unexposed areas, and then washed with ion-exchanged water. The substrate was then heated at 230° C. for 5 minutes to form green filter segments, thereby obtaining a color filter.

[0231] The color filter produced by using the photosensitive coloring composition for color filters used in the solid-state imaging element of the present invention has good adhesion, little residue, and good spectral transmittance, making it possible to produce a highly sensitive solid-state imaging element. Therefore, by using a solid-state imaging element equipped with this color filter in mobile phone cameras, in-vehicle sensors, surveillance cameras, and other devices, it will be possible to create devices with significantly improved long-distance shooting capabilities and image resolution.

Claims

1. The coloring composition contains a colorant (A), a resin-type dispersant (B), a polymerizable compound (C), a photopolymerization initiator (D) and an organic solvent, the colorant (A) contains a phthalocyanine pigment (A1), a quinophthalone pigment (A2) and a metal azo pigment (A3), and the colorant (A) accounts for 50% by weight or more and 90% by weight or less of a total solid content of the coloring composition, The phthalocyanine pigment (A1) is one selected from the group consisting of C.I. Pigment Green 36, 58, 59, 62, and 63; The quinophthalone pigment (A2) is one selected from the group consisting of C.I. Pigment Yellow 138, 231, and 233; the metallic azo pigment (A3) is one selected from the group consisting of an adduct of zinc azobarbituric acid and melamine, an adduct of nickel azobarbituric acid and melamine, and an adduct of zinc / nickel azobarbituric acid and melamine; The resin-type dispersant (B) contains a basic resin-type dispersant (B1) and an acidic resin-type dispersant (B2), A photosensitive coloring composition for a color filter used in a solid-state imaging device, characterized in that it further contains a binder resin (E) having a weight average molecular weight (Mw) of 12,000 or less (excluding the case of a resin-type dispersant (B)).

2. The photosensitive coloring composition for a color filter used in a solid-state imaging device according to claim 1, wherein the amine value of the basic resin-type dispersant (B1) is 10 to 80 mg KOH / g.

3. The photosensitive coloring composition for color filters used in solid-state imaging devices according to claim 1 or 2, characterized in that the polymerizable compound (C) contains a polymerizable compound (C1) having four or more ethylenically unsaturated double bonds, and the polymerizable compound (C1) having four or more ethylenically unsaturated double bonds is 1% by weight or more and 15% by weight or less in the total solid content of the photosensitive coloring composition.

4. A color filter for use in a solid-state imaging device, comprising a layer formed from the photosensitive coloring composition for a color filter for use in a solid-state imaging device according to any one of claims 1 to 3.

5. A solid-state imaging device comprising the color filter according to claim 4.

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