Photosensitive coloring components, color filters, image display devices, and solid-state photographic elements

Abstract

This invention provides a photosensitive coloring composition in which the desired pixel width can be obtained even at low exposure during development, and wrinkles on the pixel surface are suppressed, and the pixels are heat-resistant and the height of the stacked photospaces can be easily controlled. A photosensitive coloring composition comprises: a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the polymerizable compound (C) comprises a polyfunctional aminocarbamate (meth)acrylate (C1), and the photopolymerization initiator (D) comprises an oxime ester-based photopolymerization initiator (D2b) containing two oxime ester groups in one molecule, as represented by the following general formula (1).

Description

[Technical Field]

[0001] The present invention relates to a photosensitive coloring composition used in color filters and the like. [Previous Technology]

[0002] Regarding a color filter used as a filter in an image display device or a solid photographic element, a pattern is usually formed on a film made of a photosensitive coloring composition using steps such as photolithography.

[0003] In a liquid crystal display (LCD), a thin film transistor (TFT) substrate and a color filter substrate are arranged facing each other with a predetermined interval, and liquid crystal is sealed in the gap. If the interval is not maintained accurately, a difference in the thickness of the liquid crystal layer will occur, resulting in display defects. Therefore, a method for forming such a spacer is proposed in Patent Document 1. Patent Document 1 discloses a method for forming columnar protrusions with a diameter of 10 μm to 50 μm, called spacers, on a color filter substrate using photolithography.

[0004] As a photosensitive coloring composition forming spacers, Patent Document 2 discloses a photosensitive coloring composition comprising an extender pigment and a special monomer. Patent Document 3 discloses a photosensitive coloring composition comprising an epoxy curing agent. Patent Document 4 discloses a photosensitive coloring composition whose leveling properties are improved by adjusting the solvent composition. [Prior Art Documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2013-101234 [Patent Document 2] Japanese Patent Application Publication No. 2013-97235 [Patent Document 3] Japanese Patent Application Publication No. 2020-095194 [Patent Document 4] Japanese Patent Application Publication No. 2019-133144 [Summary of the Invention]

[0006] [Problem to be Solved by the Invention] Due to the manufacturing cost of color filters, there is a need to shorten the manufacturing step time. In this case, it is necessary to manufacture high-performance color filters with less exposure (time) than before, but with less exposure, the pixel width becomes narrower after development. Therefore, there is a need for a composition that can obtain a pixel width (hereinafter referred to as linewidth sensitivity) similar to that of the photomask with less exposure. However, in addition to the problem that the pixel width becomes narrower if the exposure is reduced to shorten the step time, previous compositions also have the problem of pixel surface wrinkling and insufficient heat resistance. In addition, when using previous compositions to form a stacked optical spacer with pixels, it is difficult to adjust its height.

[0007] The object of the present invention is to provide a photosensitive coloring composition in which the desired pixel width (linewidth sensitivity) can be obtained even with less exposure than before (low exposure), and pixel surface wrinkling is suppressed, and the pixels are heat-resistant and the height of the stacked photoresistors can be easily adjusted. [Technical means to solve the problem]

[0008] This invention relates to a photosensitive coloring composition comprising: a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the polymerizable compound (C) comprises a polyfunctional aminocarbamate (meth)acrylate (C1), and the photopolymerization initiator (D) comprises an oxime ester photopolymerization initiator (D2b) containing two oxime ester groups in one molecule, as represented by the following general formula (1). General formula (1) [Chemical 1] (wherein, in general formula (1), X1 and X2 independently represent a carbonyl bond (-CO-) or a single bond; X3 represents a single bond or a sulfur atom; R1 represents an alkyl group having 1 to 20 carbon atoms; R2 and R3 each independently represent a hydrogen atom and an alkyl group having 1 to 20 carbon atoms; R4 and R5 each independently represent an alkyl group having 1 to 20 carbon atoms)

[0009] In addition, the present invention relates to the photosensitive coloring composition, wherein the polymeric compound (C) further comprises a polymeric compound (C2) having a viscosity of less than 800 mPa·S at 25°C (except for urethane (meth)acrylate (C1)).

[0010] In addition, the present invention relates to the photosensitive coloring composition, wherein the content of the polymeric compound (C2) with a viscosity of less than 800 mPa·S at 25°C is 5% to 50% by mass in 100% by mass of the polymeric compound (C).

[0011] In addition, the present invention relates to the photosensitive coloring composition, wherein the colorant (A) comprises a phthalocyanine pigment with Al as the central metal.

[0012] In addition, the present invention relates to a color filter having: a substrate and a filter segment formed of the photosensitive coloring composition.

[0013] In addition, the present invention relates to an image display device having the aforementioned color filter.

[0014] Furthermore, the present invention relates to a solid-state photographic element having the aforementioned color filter. [Effects of the Invention]

[0015] According to the present invention, a photosensitive coloring composition can be provided, wherein even with less exposure than before (low exposure), the desired pixel width (linewidth sensitivity) can be obtained, and pixel surface wrinkling is suppressed, and the pixels have heat resistance and the height of the stacked light spacers can be easily adjusted. In addition, the present invention can provide a filter, an image display device, and a solid-state photographic element.

Implementation Method

[0017] The terms used in this application are defined. When expressed as "(meth)acrylic," "(meth)acrylate," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide," unless otherwise specified, they respectively represent "acrylic and / or methacrylic," "acrylic and / or methacrylic acid," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide." The term "CI" used in this specification refers to the Colour Index (CI). Colorants include pigments and dyes.

[0018] The photosensitive coloring composition of the present invention comprises: a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the polymerizable compound (C) comprises a polyfunctional aminocarbamate (meth)acrylate (C1), and the photopolymerization initiator (D) comprises an oxime ester-based photopolymerization initiator (D2b) containing two oxime ester groups in one molecule, as represented by the following general formula (1). By using the polyfunctional aminocarbamate (meth)acrylate (C1) and the oxime ester-based photopolymerization initiator (D2b), the photosensitive coloring composition of the present invention solves the following problems: even with low exposure during development, the desired pixel width can be obtained, and wrinkles on the pixel surface are suppressed; the pixels are heat-resistant, and the height of the stacked photospacer can be easily controlled. Furthermore, the desired pixel width is the width of the pixel formed by the photomask. In this specification, pixels that can be manufactured to be larger than the pixel width of the photomask are preferred. General formula (1) [Chemical 2] (wherein, in general formula (1), X1 and X2 independently represent carbonyl bonds (-CO-) or single bonds; X3 represents a single bond or a sulfur atom; R1 represents an alkyl group with 1 to 20 carbon atoms; R2 and R3 each independently represent a hydrogen atom and an alkyl group with 1 to 20 carbon atoms; R4 and R5 each independently represent an alkyl group with 1 to 20 carbon atoms)

[0019] The photosensitive coloring composition of the present invention is preferably used for applications such as pixels or stacked light spacers in color filters constituting image display devices or solid-state photographic elements.

[0020] <Coloring Agent> Coloring agents may include pigments or dyes. Pigments may include organic pigments and inorganic pigments. Pigments are preferably pigments with high color development and high heat resistance, and in particular, organic pigments are preferred in terms of high resistance to thermal decomposition. Hereinafter, specific examples of organic pigments will be indicated using dye index numbers.

[0021] Examples of red pigments include: CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 6 4, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181,1 84, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 2 Pigments described in Japanese Patent Application Publication No. 2014-134712 and Japanese Patent Publication No. 6368844, etc. Among these, from the viewpoints of heat resistance, light resistance and transmittance, CI Pigment Red 48: 1, 122, 177, 224, 242, 269, 254, 291, 295, 296, the pigments described in Japanese Patent Application Publication No. 2014-134712 and Japanese Patent Publication No. 6368844 are preferred, and even more preferred are CI Pigment Red 177, 254, 291, 295, 296, the pigments described in Japanese Patent Application Publication No. 2014-134712 and Japanese Patent Publication No. 6368844.

[0022] Examples of orange pigments include: CI pigment orange 36, 38, 43, 64, 71, 73, etc.

[0023] Examples of yellow pigments include: CI pigment yellow (pigment yellow) 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, 9 3. 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154 Pigments, etc., as described in Japanese Patent Application Publication No. 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, Japanese Patent Application Publication No. 2012-226110, Japanese Patent Application Publication No. 2017-171912, Japanese Patent Application Publication No. 2017-171913, Japanese Patent Application Publication No. 2017-171914, Japanese Patent Application Publication No. 2017-171915, etc. Among these, the preferred pigments are those described in CI Pigment Yellow 138, 139, 150, 185, 231, 233, and Japanese Patent Application Publication No. 2012-226110.

[0024] Examples of green pigments include: CI pigment green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, etc. Among these, CI pigment green 36, 58, 59, 62, and 63 are preferred.

[0025] Examples of blue pigments include: CI pigment blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc. Among these, CI pigment blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are preferred.

[0026] Examples of purple pigments include: CI pigment violet 1, 1:1, 2, 2:2, 33:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, 50, etc. Among these, CI pigment violet 19 and 23 are preferred.

[0027] Examples of black pigments include: CI Pigment Black 1, 6, 7, 12, 20, 31, 32, etc. Additionally, compounds described in Japanese Patent Publication No. 2010-534726, Japanese Patent Publication No. 2012-515233, Japanese Patent Publication No. 2012-515234, Japanese Patent Publication No. 1-170601, and Japanese Patent Publication No. 2-34664 may also be listed.

[0028] In this specification, the photosensitive coloring composition is preferably a photosensitive green composition comprising a green pigment and a yellow pigment. In this case, the green pigment is preferably CI Pigment Green 58 (a phthalocyanine pigment with Zn as the central metal) or CI Pigment Green 63 (a phthalocyanine pigment with Al as the central metal), and more preferably CI Pigment Green 63. The yellow pigment is preferably CI Pigment Yellow 138. Thus, for example, in LCD applications where a white light-emitting diode (LED) is used for backlighting, a high-brightness, greenest pixel can be formed.

[0029] Other inorganic pigments besides those mentioned above may include: titanium dioxide, barium sulfate, zinc white, lead sulfate, chrome yellow, zinc yellow, iron oxide (red iron oxide (III)), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, brown earth, synthetic iron black, etc.

[0030] <Pigment Micronization> When using organic pigments in colorants, it is preferable to mix them with other raw materials after micronization treatment. Examples of micronization treatment methods include wet milling, dry milling, and solvent extraction. Among these, salt milling, a type of wet milling, is preferred. The average primary particle size of the micronized organic pigment is preferably 10 nm to 80 nm, more preferably 15 nm to 70 nm. With an appropriate particle size, dispersibility is further improved, and the contrast ratio of the film is further improved. Furthermore, the average primary particle size is the average value of about 20 particles arbitrarily selected from the magnified image of a transmission electron microscope (TEM). In addition, when the longitudinal and transverse axis lengths of the particles are considered, the longitudinal axis length is used.

[0031] Salt milling refers to the following process: using batch or continuous mixing machines such as kneaders, two-rod roll mills, three-rod roll mills, ball mills, attritors, sand mills, and planetary mixers, a mixture of pigments and water-soluble inorganic salts (e.g., sodium chloride) and water-soluble organic solvents is mechanically mixed while heated, followed by washing with water to remove the water-soluble inorganic salts and organic solvents. The water-soluble inorganic salts act as a crushing aid; during salt milling, the high hardness of the inorganic salts causes the pigments to break down. By optimizing the conditions for salt milling pigments, pigments with very fine primary particle sizes, narrow particle size distributions, and sharp particle size distributions can be obtained.

[0032] During salt milling, resin may be added as needed. Examples of resins include: natural resins, modified natural resins, synthetic resins, and synthetic resins modified from natural resins. The resin is preferably solid at room temperature and insoluble in water, and more preferably partially soluble in water-soluble organic solvents. The amount of resin used is preferably 5 to 200 parts by weight relative to 100 parts by weight of pigment.

[0033] <Removal of Metals> If a specific metallic element, other than a component of the pigment, is present in large quantities in the coloring composition, it will hinder the dispersion stability over time. In addition, it may sometimes reduce heat resistance or cause a decrease in sensitivity. Furthermore, color filters made using it may sometimes generate foreign matter, which can easily lead to a decrease in brightness. The total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metallic elements) contained in the photosensitive coloring composition is preferably 500 ppm by mass or less.

[0034] The total amount of the specific metal element contained in the photosensitive coloring composition is more preferably 300 ppm by mass or less, particularly preferably 200 ppm by mass or less. Furthermore, there is no particular limitation on the lower limit of the total amount of the specific metal element, but it is preferably 1 ppm by mass or more, more preferably 5 ppm by mass or more. Within this range, a photosensitive coloring composition for a color filter that also suppresses cost, exhibits excellent storage stability, and minimizes the formation of foreign matter and light reduction can be obtained. In addition, the content of the specific metal element can be determined by inductively coupled plasma luminescence spectrophotometry (ICP).

[0035] The amount of each specific metal element contained in the photosensitive coloring composition is preferably 100 ppm by mass or less, more preferably 50 ppm by mass or less.

[0036] Furthermore, both metals constituting the pigment, such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co, and impurities that cannot effectively function should be minimized, and can be removed using the same methods as for specific metal elements. Moreover, substances that may be introduced through materials (e.g., catalysts) used in the manufacturing process of various raw materials for the photosensitive coloring composition, such as Mn, Cs, Ti, Co, Si, and Pd, are also preferably present in low concentrations.

[0037] As a method for removing colorant (A) or metal mixed in from the device during the manufacturing process, examples include the water washing method described in Japanese Patent Application Publication No. 2010-83997, Japanese Patent Application Publication No. 2018-36521, Japanese Patent Application Publication No. Hei 7-198928, Japanese Patent Application Publication No. Hei 8-333521, and Japanese Patent Application Publication No. 2009-7432, and the removal of magnetic foreign matter using a magnet described in Japanese Patent Application Publication No. 2011-48736.

[0038] <Dyes> Examples of dyes include: acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Additionally, dye derivatives or lake pigments formed by lake-forming dyes can also be listed.

[0039] The acid dye is preferably an acidic compound having an acidic group such as a sulfonic acid group or a carboxylic acid group. Furthermore, a salt-forming compound consisting of an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound is preferred. Additionally, a salt-forming compound consisting of a resin component having these functional groups and an acid dye is also preferred. Furthermore, by modifying the salt-forming compound into a sulfonylurea compound through sulfonation, a photosensitive coloring composition with excellent resistance (lightfastness, solvent resistance) can be easily obtained. Additionally, a salt-forming compound consisting of an acid dye and a compound having an onium salt group is also preferred due to its excellent resistance (lightfastness, solvent resistance). Moreover, a resin having a cationic group is preferred for compounds having onium salt groups.

[0040] Basic dyes can be used directly, but salt-forming compounds that form salts with organic acids or perchloric acid or their metal salts are preferred. Salt-forming compounds of basic dyes are preferred due to their excellent resistance (lightfastness, solvent resistance) or affinity for pigments. Furthermore, in the salt-forming compounds of basic dyes, the anionic component that acts as the anti-charge ion is preferably a salt-forming compound obtained by salting organic sulfonic acids, organic sulfuric acids, fluorine-containing phosphorus anionic compounds, fluorine-containing boron anionic compounds, cyanide-containing nitrogen anionic compounds, anionic compounds containing conjugate bases of organic acids having halogenated hydrocarbon groups, and acidic dyes. In addition, if the salt-forming compound contains polymerizable unsaturated groups in its molecule, its resistance is further improved.

[0041] The chemical structures of dyes can be derived from, for example, azo dyes, diazo dyes, azomethyl base dyes (indoaniline dyes, indophenol dyes, etc.), dipyrrole methylene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthraquinone dyes, anthraquinone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthones dyes, acridine dyes, etc.), quinone imine dyes (oxazine dyes, thiazine dyes, etc.). (e.g., aziridine dyes, polymethyl dyes (oxocyanine dyes, cyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squaric acid endothelinium dyes, croconium dyes, etc.), quinoline dyes, phthalocyanine dyes, subphthalocyanine dyes, violet ketone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, etc.) From the viewpoint of color characteristics such as hue, color separation, and color unevenness, azo dyes, succinate dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrrole methylene dyes, squaric acid lacton dyes, quinoline ketone dyes, phthalocyanine dyes, and phthalocyanine dyes are preferred, and succinate dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrrole methylene dyes, and phthalocyanine dyes are more preferred.

[0042] Colorant (A) may be used alone or in combination with two or more.

[0043] In 100% by mass of the non-volatile components of the photosensitive coloring composition, the content of colorant (A) is preferably 5% to 70% by mass, more preferably 10% to 60% by mass.

[0044] <Pigment Derivatives> Pigment derivatives may be used in the coloring composition as needed. Pigment derivatives are compounds having acidic, basic, or neutral groups in the organic pigment residues. Examples of pigment derivatives include: compounds having acidic substituents such as sulfonyl, carboxyl, or phosphate groups, and their amine salts; compounds having basic substituents such as sulfonamide groups or tertiary amine groups at the end; and compounds having neutral substituents such as phenyl or phthalimide alkyl groups. Organic pigments include, for example, diketopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, violet ketone pigments, perylene pigments, thiazine-indigo pigments, triazine pigments, benzimidazolone pigments, benzimidazolyl and other indole pigments, isoindoline pigments, isoindolineone pigments, quinoline ketone pigments, naphthol pigments, reduction pigments, metal complex pigments, azo, diazo, polyazo and other azo pigments, etc.

[0045] Specifically, diketopyrrolopyrrole pigment derivatives include those described in Japanese Patent Application Publication No. 2001-220520, WO2009 / 081930, WO2011 / 052617, WO2012 / 102399, and Japanese Patent Application Publication No. 2017-156397; phthalocyanine pigment derivatives include those described in Japanese Patent Application Publication No. 2007-226161, WO2016 / 163351, Japanese Patent Application Publication No. 2017-165820, and Japanese Patent No. 5753266; anthraquinone pigment derivatives include those described in Japanese Patent Application Publication No. 63-26. The pigment derivatives described in Japanese Patent Publication No. 4674, Japanese Patent Application Publication No. 09-272812, Japanese Patent Application Publication No. 10-245501, Japanese Patent Application Publication No. 10-265697, Japanese Patent Application Publication No. 2007-079094, and Manual No. WO2009 / 025325; quinacridone-based pigment derivatives include those described in Japanese Patent Application Publication No. 48-54128, Japanese Patent Application Publication No. 03-9961, and Japanese Patent Application Publication No. 2000-273383; dioxazine-based pigment derivatives include those described in Japanese Patent Application Publication No. 2011-162662; thiazide-indigo-based pigment derivatives include... The following are examples of pigment derivatives described in Japanese Patent Application Publication No. 2007-314785: Triazine pigment derivatives include those described in Japanese Patent Application Publication Nos. 61-246261, 11-199796, 2003-165922, 2003-168208, 2004-217842, and 2007-314681; Benzoindole pigment derivatives include those described in Japanese Patent Application Publication No. 2009-57478; Quinophthalone pigment derivatives include those described in Japanese Patent Application Publication No. 2003-167112. Pigment derivatives described in Japanese Patent Publication No. 2006-291194, Japanese Patent Publication No. 2008-31281, and Japanese Patent Publication No. 2012-226110; Naphthol-based pigment derivatives include those described in Japanese Patent Publication No. 2012-208329 and Japanese Patent Publication No. 2014-5439; Azo-based pigment derivatives include those described in Japanese Patent Publication No. 2001-172520 and Japanese Patent Publication No. 2012-172092; Acidic substituents [compounds having acidic substituents] include those described in Japanese Patent Publication No. 2004-307854;Basic substituents [compounds having basic substituents] can be exemplified by pigment derivatives described in Japanese Patent Application Publications Nos. 2002-201377, 2003-171594, 2005-181383, and 2005-213404. Furthermore, in these documents, pigment derivatives are sometimes referred to as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds, etc. The compounds having substituents such as acidic, basic, or neutral groups in the organic pigment residues have the same meaning as pigment derivatives.

[0046] The pigment derivatives may be used alone or in combination of two or more.

[0047] The amount of pigment derivative used is preferably 1 to 100 parts by mass relative to 100 parts by mass of organic pigment, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass.

[0048] By adding pigment derivatives to the pigment and performing micronization treatments such as acid gelatinization, acid slurrying, dry grinding, salt grinding, and solvent salt grinding, the pigment derivatives are adsorbed onto the pigment surface. Compared with the case where no pigment derivatives are added, the primary particles of the pigment can be further micronized.

[0049] <Resin-type dispersant> The photosensitive coloring composition of the present invention may contain a dispersing resin (G). The dispersing resin (G) has: a colorant-affinity site adsorbed on the colorant (A), and a milding site with high affinity for components other than the colorant and causing the dispersed particles to stereorepel each other. Dispersing resins (G) may include, for example: urethane-based dispersants such as polyurethanes; polycarboxylic acid esters such as polyacrylates, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyurethane phosphates, hydroxyl-containing polycarboxylic acid esters, or modified forms thereof; amides or their salts formed by the reaction of poly(lower alkylimides) with polyesters having free carboxyl groups; (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, polyvinylpyrrolidone, etc.; polyesters, modified polyacrylates, ethylene oxide / propylene oxide addition compounds, phosphate esters, etc. In addition, examples of polymeric dispersion resins with basic functional groups include: nitrogen-containing graft copolymers, acrylic block copolymers or urethane polymeric dispersion resins with nitrogen-containing functional groups including tertiary amine groups, quaternary ammonium salt groups, nitrogen-containing heterocycles, etc. in the side chains.

[0050] Commercially available resin-type dispersion resins include, for example, Disperbyk - 101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, manufactured by BYK-Chemie Japan. 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164, or Anti-Terra-U, 203, 204, or BYK-P104, P104S, 220S, LPN6919, LPN21116, LPN21324, or Lactimon, Lactimon-WS, or Bykumen, etc., and SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20... manufactured by Lubrizol Corporation of Japan. 000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., BASF Japan. The following models are manufactured by Japan: EFKA - 46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450. Models 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisper PA111, PB711, PB821, PB822, PB824, etc., manufactured by Ajinomoto Precision Technology Co., Ltd.

[0051] The amount of dispersion resin (G) used relative to the colorant (A) is preferably about 3% to 200% by mass, more preferably about 5% to 100% by mass. If used in appropriate amounts, film-forming properties can be improved.

[0052] [Alkali-soluble resin (B)] The alkali-soluble resin (B) is an adhesive resin, preferably used for patterning a film using photolithography. The alkali-soluble resin (B) has alkali-soluble groups. Examples of alkali-soluble groups include carboxyl groups, phosphate groups, sulfonic acid groups, hydroxyl groups, phenolic hydroxyl groups, etc. Among these, carboxyl groups are preferred. Alkali-soluble resin (B) can be broadly classified into non-photosensitive alkali-soluble resin (B2) and photosensitive alkali-soluble resin (B1).

[0053] (Non-photosensitive alkali-soluble resin (B2)) Examples of non-photosensitive alkali-soluble resins (B2) include: acrylic resins with acidic groups, α-olefin / maleic acid (anhydride) copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / maleic acid (anhydride) copolymers. Among these, acrylic resins with acidic groups and styrene / styrene sulfonic acid copolymers are preferred.

[0054] (Photosensitive alkali-soluble resin (B1)) The photosensitive alkali-soluble resin (B1) is an alkali-soluble resin having polymerizable unsaturated groups. The photosensitive alkali-soluble resin (B1) is preferably a resin synthesized using the method shown in (i) or (ii) below. Through curing using active energy lines, the resin undergoes three-dimensional cross-linking, increasing the cross-linking density and improving chemical resistance.

[0055] [Method (i)] Method (i) may be exemplified by the following method: First, a polymer containing an epoxy group monomer and other monomers is synthesized. Then, a monomer containing a monocarboxyl group is added to the epoxy group of the polymer, and a polyacid anhydride is reacted with the generated hydroxyl group to obtain a photosensitive alkali-soluble resin.

[0056] Examples of epoxy-containing monomers include glycidyl methacrylate, methyl glycidyl methacrylate, 2-glycidyloxyethyl methacrylate, 3,4-epoxybutyl methacrylate, and 3,4-epoxycyclohexyl methacrylate. Among these, glycidyl methacrylate is preferred from the viewpoint of reactivity.

[0057] Other monomers include, for example: methyl methacrylate, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate, n-butyl methacrylate, isobutyl methacrylate, tert-butyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl methacrylate, stearyl methacrylate, lauryl methacrylate, tetrahydrofurfuryl methacrylate, isobornyl methacrylate, phenyl methacrylate, benzyl methacrylate, phenoxyethyl methacrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethylene oxide (meth) (Meth) acrylates include: EO-modified cresol acrylates, n-nonylphenoxy polyethylene glycol acrylates, phenoxy ethyl acrylates, ethoxylated phenyl acrylates, EO-modified (meth) acrylates of phenol, EO-modified (meth) acrylates of p-cumylphenol or propylene oxide (PO)-modified (meth) acrylates, EO-modified (meth) acrylates of nonylphenol, PO-modified (meth) acrylates of nonylphenol, etc.; (meth) acrylamides, N,N-dimethyl (meth) acrylamides, N,N-diethyl (meth) acrylamides, N-isopropyl (meth) acrylamides, diacetone (meth) acrylamides, or acrylmorpholine, etc.; styrene, or α-methylstyrene, etc.; ethyl vinyl ethers, n-propyl vinyl ethers, isopropyl vinyl ethers, n-butyl vinyl ethers, or isobutyl vinyl ethers, etc. Vinyl acetate or vinyl propionate and other fatty acid vinyl esters; cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimide phenyl)methane, N,N'-1,3-extrin-phenyldimaleimide, N,N'-1,4-extrin-phenyldimaleimide, N-(1-pyrene)maleimide, N-(2,4, N-substituted maleimides include 6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimido-3-maleimide benzoate, N-succinimido-3-maleimide propionate, N-succinimido-4-maleimide butyrate, N-succinimido-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimide acridine.2-(meth)propenyloxyethyl phosphate, compounds formed by reacting a phosphate esterifying agent such as phosphoric acid ester with the hydroxyl group of a hydroxyl-containing monomer described below, and other monomers containing phosphate ester groups.

[0058] Monomers containing a monocarboxyl group can be listed as follows: (meth)acrylic acid, crotonic acid, o-vinylbenzoic acid, m-vinylbenzoic acid, p-vinylbenzoic acid, α-haloalkyl, alkoxy, halogen, nitro, cyano substituted monocarboxylic acids, etc.

[0059] Examples of polybasic acid anhydrides include: tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. Additionally, depending on the need, tricarboxylic anhydrides such as trimellitic anhydride and tetracarboxylic dianhydrides such as pyromellitic anhydride can be used to hydrolyze the remaining anhydride groups.

[0060] Alternatively, as a method similar to method (i), for example, the following method can be used: synthesizing a polymer of a carboxyl-containing monomer and other monomers. Subsequently, a portion of the carboxyl group of the polymer is added to an epoxy-containing monomer to obtain a photosensitive alkali-soluble resin.

[0061] [Method (ii)] Method (ii) may include, for example, the following method: synthesizing a polymer of a hydroxyl-containing monomer, a monocarboxyl-containing monomer, and other monomers; and then reacting the isocyanate group of the isocyanate-containing monomer with the hydroxyl group of the polymer.

[0062] Examples of hydroxyl-containing monomers include: 2-hydroxyethyl methacrylate, 2-hydroxypropyl methacrylate, or 3-hydroxypropyl methacrylate, 2-hydroxybutyl methacrylate, or 3-hydroxybutyl methacrylate, or 4-hydroxybutyl methacrylate, glycerol mono(meth)acrylate, or cyclohexanediol mono(meth)acrylate, etc., which are hydroxyalkyl methacrylates. Additionally, examples include polyether mono(meth)acrylates formed by the addition polymerization of hydroxyalkyl methacrylates with ethylene oxide, propylene oxide, and / or butane oxide, or polyester mono(meth)acrylates formed by the addition polymerization with poly(γ-valerol), poly(ε-caprolactone), and / or poly(12-hydroxystearic acid). Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred in terms of minimizing the generation of foreign matter in the coating. Furthermore, glycerol mono(meth)acrylate is preferred in terms of light sensitivity.

[0063] Monomers containing isocyanate groups include: 2-(meth)acryloxyethyl isocyanate, 2-(meth)acryloxyethyl isocyanate, or 1,1-bis[methacryloxy]ethyl isocyanate, etc.

[0064] Monomers containing a single carboxyl group and other monomers may use the monomers already illustrated.

[0065] The raw materials used in the synthesis of photosensitive alkali-soluble resins may be used individually or in combination of two or more.

[0066] In addition, the photosensitive alkali-soluble resin may also be a resin formed by giving polymerizable unsaturated groups to the non-photosensitive alkali-soluble resin described above.

[0067] The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000. Furthermore, the Mw / Mn value is preferably 10 or less. With a suitable Mw, the adhesion to the substrate and the alkali developability are improved.

[0068] To impart alkali-soluble solubility, the acid value of the alkali-soluble resin (B) is preferably 50 mgKOH / g to 200 mgKOH / g, more preferably 70 mgKOH / g to 180 mgKOH / g, and even more preferably 90 mgKOH / g to 170 mgKOH / g. With an appropriate acid value, alkali-soluble solubility is improved, and residues can be suppressed. The straightness of the pattern is improved.

[0069] From the viewpoint of developer solubility, the content of alkali-soluble resin (B) in the non-volatile components of the photosensitive coloring composition is preferably 5% to 60% by mass, more preferably 10% to 40% by mass.

[0070] In this specification, thermoplastic resins may be used in conjunction with adhesive resins other than alkali-soluble resins.

[0071] <Thermoplastic Resins> 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, cellulose resins, polyethylene (high-density polyethylene (HDPE), low-density polyethylene (LDPE)), polybutadiene, and polyimide resins, etc.

[0072] <Polymerizable Compound (C)> The photosensitive coloring composition of the present invention comprises a polyfunctional aminocarbamate (meth)acrylate (C1) as a polymerizable compound (C). The polymerizable compound (C) is a monomer or oligomer having polymerizable unsaturated groups. Examples of polymerizable unsaturated groups include vinyl, (meth)acrylyl, (meth)allyl, etc. The number of polymerizable unsaturated groups in the polymerizable compound (C) is one or more, preferably two or more, more preferably three or more. Furthermore, the upper limit for the number of polymerizable unsaturated groups is 20. Furthermore, the polymeric compound (C) preferably includes one or more of the following: polymeric compound (C2) with a viscosity of 800 mPa·S or less at 25°C (excluding urethane (meth)acrylate (C1)); polymeric compound (C3) having an acid group (excluding (C1) and (C2)); and other polymeric compounds (C4) (excluding (C1), (C2) and (C3)). More preferably, it is polymeric compound (C2) with a viscosity of 800 mPa·S or less at 25°C.

[0073] (Polyfunctional urethane (meth)acrylate (C1)) The polyfunctional urethane (meth)acrylate (C1) is a (meth)acrylate having an urethane bond, and is particularly preferably an urethane (meth)acrylate having an aliphatic site. Examples of aliphatic sites include chain hydrocarbon groups and saturated cyclic hydrocarbon groups. Using an urethane (meth)acrylate (C1) with an aliphatic site allows for both improved heat resistance and suppression of pixel wrinkling. Furthermore, the lower viscosity of the urethane (meth)acrylate (C1) with an aliphatic site helps control the height of the laminated optical spacers.

[0074] The urethane (meth)acrylate (C1) having an aliphatic site is not limited to having the aforementioned site; for example, reaction products of aliphatic diisocyanates and hydroxyl-containing (meth)acrylates can be listed. In particular, urethane (meth)acrylate (C1) with a linear aliphatic diisocyanate as the reactant further improves heat resistance.

[0075] Examples of hydroxyl-containing (meth)acrylates include: 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, di-trimethylolpropane 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-acrylic propyl methacrylate, reaction products of epoxy-containing compounds with carboxyl esters of (meth)acrylate, and hydroxyl-containing polyol polyacrylates, etc.

[0076] In addition, examples of polyfunctional isocyanates include: toluene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, polyisocyanate, etc.

[0077] Commercially available products of carbamate (meth)acrylate (C1) include UA-306H, UA-306I, and UA-510H manufactured by Kyoei Chemical Co., Ltd.

[0078] The content of urethane (meth) acrylate (C1) is preferably 5% to 95% by mass in 100% by mass of polymeric compound (C), more preferably 5% to 80% by mass.

[0079] (A polymeric compound (C2) with a viscosity of 800 mPa·S or less at 25°C) If the photosensitive coloring composition contains a polymeric compound (C2) with a viscosity of 800 mPa·S or less at 25°C (excluding urethane (meth)acrylate (C1)) (hereinafter referred to as polymeric compound (C2)), the fluidity of the film during solvent evaporation in the drying step can be improved, thus making it easier to adjust the height of the laminated photoresist, which is preferable. Furthermore, the height adjustment can also be performed by using a solvent with a slow evaporation rate, but this has the disadvantage of becoming a residual solvent and reducing the strength of the laminated photoresist.

[0080] Polymerizable compounds (C2) include, for example, tricyclodecane dimethylol di(meth)acrylate, bisphenol EO-modified di(meth)acrylate, polypropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate, etc. Commercially available examples of these include, for example, M-309, M-310, and M-450 manufactured by Toa Synthetic Co., Ltd., and A-DCP manufactured by Shin-Nakamura Chemical Co., Ltd.

[0081] The content of the polymeric compound (C2) is preferably 5% to 50% by mass in 100% by mass of the polymeric compound (C), and more preferably 5% to 30% by mass.

[0082] The polymerizable compound (C2) preferably has two or more polymerizable unsaturated groups, more preferably three or more. This makes it easier to balance linewidth sensitivity and thickness ratio control at low exposure levels. Furthermore, regarding the thickness ratio, the thickness (a) of the pixel shown in the cross-sectional view of the color filter (Fig. 2) and the thickness (b) of the stacked photoresist on the black matrix are measured using a contact thickness gauge, and the thickness ratio is calculated in the form of (b / a) × 100.

[0083] (Polymerizable compounds with acid groups (C3)) Among polymerizable compounds (C3) with acid groups, examples of acid groups include: sulfonic acid group, carboxyl group, phosphate group, etc.

[0084] Polymerizable compounds (C3) containing acid groups include, for example: poly(meth)acrylates containing free hydroxyl groups of polyols and (meth)acrylic acid, esters of poly(meth)acrylates and dicarboxylic acids; esters of polycarboxylic acids and monohydroxyalkyl esters of (meth)acrylic acid, etc. Specific examples include: monohydroxy oligoacrylates or monohydroxy oligomethyl methacrylates such as trimethylolpropane diacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate; monoesters containing free carboxyl groups with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; 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; and oligoesters containing free carboxyl groups with monohydroxy monoacrylates or monohydroxy monomethyl methacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0085] Other polymeric compounds (C4) include, for example: pentaerythritol penta(meth)acrylate and pentaerythritol hexa(meth)acrylate, ethoxylated bisphenol A diacrylate, bis-(2-acryloyloxyethyl)isocyanurate and tri-(2-acryloyloxyethyl)isocyanurate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate, neopentyl glycol diacrylate of hydroxypentanoic acid, etc.

[0086] The polymeric compound (C) may be used alone or in combination with two or more.

[0087] The amount of polymeric compound (C) is preferably 1% to 50% by mass in 100% by mass of the non-volatile components of the photosensitive coloring composition, and more preferably 2% to 40% by mass. If the amount is appropriately adjusted, the curing and developing properties are further improved.

[0088] <Photopolymerization Initiator (D)> The photopolymerization initiator (D) comprises an oxime ester-based photopolymerization initiator (D2b) containing two oxime ester groups in one molecule, and may be used in conjunction with other photopolymerization initiators as needed.

[0089] (Oxime Ester Photopolymerization Initiator (D2)) Oxime ester compounds cause the NO bond of the oxime to break by absorbing ultraviolet light, generating imine radicals and alkoxy radicals. These radicals further decompose to generate highly reactive radicals, thus enabling pattern formation with low exposure. When the colorant concentration of a photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may decrease, resulting in lower film curing. However, oxime ester compounds are preferred due to their high efficiency. Examples of oxime ester photopolymerization initiators (D2) include compounds containing one oxime ester group per molecule (D2a) and compounds containing two oxime ester groups per molecule (D2b). In this specification, in terms of preventing the linewidth of pixels from becoming too narrow under low exposure conditions (also known as linewidth sensitivity), compounds containing two oxime ester groups per molecule (D2b) are more preferred.

[0090] 〔Compounds containing two oxime ester groups in one molecule (D2b)〕 Oxime ester-based photopolymerization initiators (D2b) containing two oxime ester groups in one molecule include, for example, compounds described in Japanese Patent Application Publication No. 2005-215378, Japanese Patent Application Publication No. 2011-105713, Japanese Patent Application Publication No. 2017-523465, and Japanese Patent Application Publication No. 2021-011486. ​​In this specification, compounds represented by the following general formula (1) are preferred.

[0091] General Formula (1) [Chemical 3] (wherein, in general formula (1), X1 and X2 independently represent carbonyl bonds (-CO-) or single bonds; X3 represents single bonds or sulfur atoms; R1 represents alkyl groups with 1 to 20 carbon atoms; R2 and R3 independently represent hydrogen atoms and alkyl groups with 1 to 20 carbon atoms; R4 and R5 independently represent alkyl groups with 1 to 20 carbon atoms)

[0092] In general formula (1), from the viewpoint of solubility in organic solvents, it is preferred that at least one of X1 and X2 is a carbonyl bond (-CO-), and more preferably both X1 and X2 are carbonyl bonds (-CO-).

[0093] In general formula (1), R1 represents an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms can be any of a linear, branched, cyclic, or combination thereof alkyl group, and can also be an alkyl group substituted with a halogen atom, amino group, nitro group, etc. Examples include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl group, isopentyl, pentyl group, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, cyclohexylmethyl, etc. Among these, ethyl, propyl, and isopropyl are preferred.

[0094] In general formula (1), the alkyl groups with 1 to 20 carbon atoms in R2 and R3 can be any type of linear, branched, cyclic, or combination thereof alkyl groups. Alternatively, they can be alkyl groups substituted with halogen atoms, amino groups, nitro groups, etc. Examples include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, amyl group, isopentyl, pentyl group, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, nonyl, decyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, cyclohexylmethyl, etc. Preferably, pentyl, hexyl, heptyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, cyclohexylmethyl. Of these, regarding R2 and R3, from the viewpoint of solubility in organic solvents, at least one is preferably a straight-chain alkyl group having 1 to 20 carbon atoms, and from the viewpoint of solubility in organic solvents and suppression of water stains, it is more preferably a straight-chain alkyl group having 1 to 20 carbon atoms and a cyclic alkyl group having 1 to 20 carbon atoms.

[0095] In general formula (1), R4 and R5 each independently represent an alkyl group having 1 to 20 carbon atoms. The alkyl group having 1 to 20 carbon atoms is the same as described above. Among them, from the viewpoint of reactivity, methyl, ethyl, propyl, and isopropyl are preferred.

[0096] Of these, from the viewpoint of reactivity, R4 and R5 are preferably methyl, ethyl, or phenyl, and more preferably methyl or ethyl.

[0097] There are no particular limitations on the method of manufacturing the compound represented by general formula (1), and known methods may be used. For example, the methods described in Japanese Patent Publication No. 2017-523465 and Japanese Patent Publication No. 2021-011486 may be used.

[0098] Hereinafter, specific examples of compounds (D2b) containing two oxime ester groups in one molecule are shown. However, the present invention is not limited to these examples.

[0099] [Chemistry 4] Chemical formula (2) Chemical formula (3) Chemical formula (4)

[0100] Of the chemical formulas (2) to (4), from the viewpoint of good linewidth sensitivity, compounds of chemical formulas (2) and (4) are preferred.

[0101] The content of the compound (D2b) containing two oxime ester groups per molecule is preferably 0.1 to 20 parts by mass, more preferably 0.5 to 10 parts by mass, relative to 100 parts by mass of the non-volatile component of the coloring composition. If the amount is adjusted appropriately, the linewidth sensitivity can be further improved.

[0102] [A compound containing one oxime ester group in one molecule (D2a)] In this invention, linewidth sensitivity is further improved by using a compound containing two oxime ester groups in one molecule (D2b) and a compound containing one oxime ester group in one molecule (D2a). Commercially available examples of compounds (D2a) containing one oxime ester group per molecule include: IRGACURE OXE-01, 02, and 03 manufactured by BASF Japan; Adeka arkls N-1919, NCI-831, and 930 manufactured by ADEKA; TRONLYTR-PBG-301, 304, 305, 309, 314, 358, 380, 365, 610, 3054, and 3057 manufactured by Changzhou Qiangli New Materials Co., Ltd.; OMNIRAD 1312, 1314, and 1316 manufactured by IGM Resins; SPI-02, 03, 04, 06, and 07 manufactured by Samyang Corporation; and Daito Chemical Co., Ltd. Products such as DFI-020 and EOX-01 manufactured by Chemix.

[0103] Compounds containing one oxime ester group in one molecule (D2a) include, for example, the following compounds. However, the present invention is not limited to these.

[0104] [Chemistry 5] Chemical formula (5) Chemical formula (6)

[0105] [Chemistry 6] Chemical formula (7) Chemical formula (8)

[0106] The methods for manufacturing compounds of chemical formulas (5) to (8) can be exemplified by methods described in Japanese Patent Publication No. 2004-534797, Japanese Patent Application Publication No. 2008-80068, Japanese Patent Publication No. 2012-526185, International Publication No. 2015 / 036910, International Publication No. 2015 / 152153, Japanese Patent Publication No. 2016-504270, and Japanese Patent Publication No. 2017-512886.

[0107] A compound containing one oxime ester group (D2a) per molecule can be used alone or in combination with two or more. The preferred content of the compound containing one oxime ester group (D2a) added is 0 to 10 parts by mass relative to 100 parts by mass of the non-volatile components of the coloring composition, more preferably 0.1 to 5 parts by mass. With appropriate formulation, the linewidth sensitivity is further improved, and the bulk density is further reduced.

[0108] (Photopolymerization initiator with a fluorene backbone but without oxime ester groups (D1)) In this specification, as described above, the linewidth sensitivity is further improved by using a compound containing two oxime ester groups (D2b) in one molecule and a compound containing one oxime ester group (D2a) in one molecule, and is therefore preferred. Furthermore, in this specification, the linewidth sensitivity is also further improved by using a compound containing two oxime ester groups (D2b) in one molecule, a photopolymerization initiator with a fluorene backbone but without oxime ester groups (D1), and a compound containing one oxime ester group (D2a) in one molecule, and is therefore preferred.

[0109] (Photopolymerization initiator (D1) represented by general formula (2))

[0110] General Formula (2) [Chemistry 7]

[0111] (In general formula (2), R1 and R2 independently represent hydrogen atoms or alkyl groups with 1 to 8 carbon atoms; R3 represents hydrogen atoms or monovalent substituents)

[0112] R1 and R2 independently represent hydrogen atoms or alkyl groups having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms can be straight-chain, branched, or cyclic, or a group formed by these bonds. Examples include: methyl, ethyl, propyl, isopropyl, butyl, isobutyl, tert-butyl, pentyl, isopentyl, hexyl, heptyl, octyl, 2-ethylhexyl, cyclopentyl, cyclopentylmethyl, cyclohexyl, cyclohexylmethyl, cyclohexylmethyl, etc. From the viewpoint of suppressing water stains and the shape of the pattern, a straight-chain alkyl group having 3 to 8 carbon atoms is preferred, and a straight-chain alkyl group having 4 to 6 carbon atoms is more preferred.

[0113] R3 represents a hydrogen atom or any monovalent substituent. Examples of monovalent substituents include: alkyl groups with 1 to 20 carbon atoms such as methyl and ethyl; alkoxy groups with 1 to 20 carbon atoms such as methoxy and ethoxy; halogen atoms such as F, Cl, Br, and I; alkyl groups with 1 to 20 carbon atoms; alkyl ester groups with 1 to 20 carbon atoms; alkoxy carbonyl groups with 1 to 20 carbon atoms; halogenated alkyl groups with 1 to 20 carbon atoms; aromatic cyclic groups with 4 to 20 carbon atoms; amino groups; aminoalkyl groups with 1 to 20 carbon atoms; hydroxyl groups; nitro groups; cyano groups; benzoyl groups (which may have substituents); and thenoyl groups (which may have substituents). Examples of substituents that can be present in benzoyl or thiophenemethyl groups include alkyl groups with 1 to 10 carbon atoms, alkoxy groups with 1 to 10 carbon atoms, and alkoxycarbonyl groups with 1 to 10 carbon atoms. Among these, from the viewpoint of free radical generation efficiency, hydrogen atoms and nitro groups are preferred, and hydrogen atoms are more preferred.

[0114] The method for manufacturing the compound (D1) represented by general formula (2) can be exemplified by methods described in Japanese Patent Publication No. 2019-507108 and Japanese Patent Publication No. 2019-528331.

[0115] Hereinafter, specific examples of compounds (D1) represented by general formula (2) are shown. However, the present invention is not limited to these.

[0116] Chemical formula (9) [Chemistry 8]

[0117] (Other Photopolymerization Initiators (D3)) Other photopolymerization initiators (D3) include, for example: 4-phenoxydichloroacetophenone, 4-tert-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinylpropane-1-one, 2-(dimethylamino)-1-[4-(4-morpholinyl)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-] [(4-morpholino)phenyl]-1-butanone and other acetophenone compounds; benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzoin dimethyl ketal and other benzoin-based compounds; benzophenone, benzoylbenzoic acid, methyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyl diphenyl sulfide, or 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone and other benzophenone-based compounds; thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropyl... Thioxanone, 2,4-diisopropylthioxanone, or 2,4-diethylthioxanone and other thioxanone compounds; 2,4,6-trichloro-triazine, 2-phenyl-4,6-bis(trichloromethyl)-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-triazine, 2-piperyl-4,6-bis(trichloromethyl)-triazine, 2,4-bis(trichloromethyl)-6-styryl-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl) Triazine compounds such as 2-(4-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-triazine, 2,4-trichloromethyl-(piperyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthroquinone, camphorquinone, and ethylanthraquinone; borate ester compounds; imidazole compounds; or titanium ceramsite compounds, etc.

[0118] The photopolymerization initiator (D) can be used alone or in combination with two or more.

[0119] The content of photopolymerization initiator (D) is preferably 0 to 10 parts by mass relative to 100 parts by mass of the non-volatile components of the coloring composition, more preferably 0.1 to 5 parts by mass. If the amount is adjusted appropriately, the linewidth sensitivity is further improved and the bulk density is further reduced.

[0120] <Sensitizer> The photosensitive coloring composition of the present invention may contain a sensitizer. Examples of sensitizers include: unsaturated ketones represented by chalcone derivatives, dibenzalacetone, etc.; 1,2-dione derivatives represented by benzoin or camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthones derivatives, thioxanthones derivatives, xanthonesone derivatives, thioxanthonesone derivatives, coumarin derivatives, coumarinone derivatives, anthocyanin derivatives, oxazine derivatives, etc.; polymethyl pigments such as acridine derivatives, azazine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squaric acid lactone derivatives, porphyrin derivatives, tetraphenylbenzene derivatives, etc. Polophore derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxolinoporphyrazine derivatives, naphthylphthalocyanine derivatives, phthalocyanine derivatives, pyranonium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spiroxazine derivatives, thiospiropyran derivatives, metal aromatic hydrocarbon complexes, organorruthenium complexes, or Michler's ketones. These include ketone derivatives, α-acetoxy esters, acetylphosphine oxide, methyl phenyl glyoxylate, benzopyrene, 9,10-phenanthroquinone, camphorquinone, ethyl anthraquinone, 4,4'-diethyl isophthalophenone, 3,3'-tetra(tert-butylperoxycarbonyl)benzophenone or 4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc. Among these, thioxanone derivatives, mifepristone derivatives, and carbazole derivatives are preferred. Specifically, more preferred are 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, etc.

[0121] Sensers can be used alone or in combination with two or more.

[0122] The content of the sensitizer is preferably 3 to 60 parts by mass relative to 100 parts by mass of the photopolymerization initiator (D), more preferably 5 to 50 parts by mass. If it is contained in an appropriate amount, the curing property and developability will be further improved.

[0123] <Thermosetting Compound> The photosensitive coloring composition of the present invention may contain a thermosetting compound. Therefore, during the heating step, the thermosetting compound reacts, increasing the crosslinking density and thus improving heat resistance.

[0124] The thermosetting compound may also be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. Examples of thermosetting compounds include: epoxy compounds, oxetane compounds, benzoguanidine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0125] The content of the thermosetting compound is preferably 0.5% to 50% by mass in 100% by mass of the non-volatile components of the photosensitive coloring composition, and more preferably 1% to 40% by mass.

[0126] <Thiol-based chain transfer agent> The photosensitive coloring composition may contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. If the thiol-based chain transfer agent is used in conjunction with a photopolymerization initiator, sulfur radicals that are not easily hindered by oxygen-induced polymerization are generated during free radical polymerization after light irradiation, thereby increasing the sensitivity of the photosensitive coloring composition.

[0127] The thiol-based chain transfer agent is preferably a polyfunctional thiol having two or more thiol groups (SH groups). Furthermore, the thiol-based chain transfer agent is more preferably having four or more SH groups. Increasing the number of functional groups facilitates photocuring from the surface of the film to its deepest part.

[0128] Examples of polyfunctional thiols include: hexane dithiol, decane dithiol, 1,4-butanediol dithiopropionate, 1,4-butanediol dithioglycolate, ethylene glycol dithioglycolate, ethylene glycol dithiopropionate, trimethylolpropane trithioglycolate, trimethylolpropane trithiopropionate, trimethylolpropane tri(3-mercaptobutyrate), pentaerythritol tetrathioglycolate, pentaerythritol tetrathiopropionate, tri(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-triazine, etc., preferably including: ethylene glycol dithiopropionate, trimethylolpropane trithiopropionate, pentaerythritol tetrathiopropionate.

[0129] Thiol chain transfer agents can be used alone or in combination with two or more.

[0130] The content of the thiol chain transfer agent is preferably 1% to 10% by mass in 100% by mass of the non-volatile components of the photosensitive coloring composition, and more preferably 0.1% to 3% by mass. If it is contained in an appropriate amount, the photosensitivity and cone shape will be improved, and wrinkles will be less likely to occur on the surface of the film.

[0131] <Polymerization Inhibitor> The photosensitive coloring composition may contain a polymerization inhibitor. As a result, photosensitivity caused by diffraction of light from the mask can be suppressed during exposure in photolithography, thus making it easier to obtain patterns of the desired shape.

[0132] Examples of polymerization inhibitors include: alkyl catechols such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol, etc.; alkyl catechol compounds such as 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylcatechol, etc. Alkylresorcinol compounds such as 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, and 4-tert-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trinonylphenylphosphite; pyroglucinol, etc.

[0133] The content of the polymerization inhibitor in the non-volatile components of the photosensitive coloring composition is preferably 0.0005 parts by weight to 0.2 parts by weight. If it is present in an appropriate amount, it is easy to obtain a good pattern shape.

[0134] <UV Absorber> The photosensitive coloring composition may contain a UV absorber. Examples of UV absorbers include: benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds. In addition, UV absorbers may also be oligomers or polymers.

[0135] The content of the ultraviolet absorber is preferably 5% to 70% by mass in a total of 100% by mass of the photopolymerization initiator and the ultraviolet absorber. If it is contained in an appropriate amount, the resolution after development will be further improved.

[0136] Furthermore, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1% to 20% by mass of the non-volatile components in the photosensitive coloring composition, within 100% by mass. If an appropriate amount is contained, the adhesion between the substrate and the film is further improved, and good resolution can be obtained.

[0137] As benzotriazole compounds, examples include: 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-tert-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tert-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 5% 2-methoxy-1 A mixture of methyl ethyl acetate with 95% phenylpropionic acid and 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy and C7-9 side chain and straight chain alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl-3-(3-(2) The reaction products of H-benzotriazol-2-yl)-5-tert-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl) -6-tert-butyl-4-methylphenol, 2-(3,5-di-tert-pentyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)phenyl]propionate.

[0138] As triazine compounds, examples 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, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidyl The reaction products of oleate esters, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, etc.

[0139] As benzophenone compounds, examples include: 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octyloxybenzophenone, 2,2'-di-hydroxy-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.

[0140] As salicylate ester compounds, examples include: phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, etc.

[0141] The content of the ultraviolet absorber is preferably 5% to 70% by mass in a total of 100% by mass of the photopolymerization initiator and the ultraviolet absorber. If it is contained in an appropriate amount, it is easy to obtain a good pattern shape. In addition, when the photosensitive coloring composition contains a sensitizer, the content of the photopolymerization initiator includes the content of the sensitizer.

[0142] <Antioxidant> The photosensitive coloring composition may contain an antioxidant. The antioxidant prevents yellowing of the film formed from the photosensitive coloring composition due to oxidation caused by thermal steps during thermosetting or indium tin oxide (ITO) annealing, and suppresses the decrease in film transmittance. Especially when the colorant concentration of the photosensitive coloring composition is high, the content of photopolymerizable compounds (D) is relatively reduced. Therefore, if this is addressed by increasing the amount of photopolymerization initiator or adjusting the formulation of thermosetting compounds, the film is prone to yellowing. Therefore, by including an antioxidant, yellowing caused by oxidation during the heating step can be prevented, and the decrease in film transmittance can be suppressed.

[0143] Antioxidants are compounds that have free radical scavenging or peroxide decomposition functions. Examples of antioxidants include hindered phenolic compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, and hydroxylamine compounds. Furthermore, antioxidants are preferably compounds that do not contain halogen atoms.

[0144] Antioxidants (L) can be used alone or in combination with two or more.

[0145] The content of antioxidant (L) is preferably 0.5% to 5.0% by mass in 100% by mass of the non-volatile components of the photosensitive coloring composition. If it is present in an appropriate amount, the transmittance, spectral characteristics and sensitivity will be improved.

[0146] <Leveling Agent> The photosensitive coloring composition may contain a leveling agent. This further improves the wettability of the film to the transparent substrate and the drying properties of the film during film formation. Examples of leveling agents include: silicone-based surfactants, fluorinated surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, etc.

[0147] Examples of silicone surfactants include linear polymers containing siloxane bonds, or modified siloxane polymers with organic groups introduced into the side chains or ends.

[0148] Commercially available products include, for example: BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie, and Toray Dow Corning. The following models are manufactured by Corning: FZ-7002, 2110, 2122, 2123, 2191, 5609; and by Shin-Etsu Chemical Industry Co., Ltd.: X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

[0149] Fluorine-based surfactants include, for example, surfactants or leveling agents having fluorocarbon chains.

[0150] Commercially available products include: Surflon S-242, 243, 420, 611, 651, 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, 576, R-40-LM, R-41, RS-72-K, DS-21 manufactured by DIC Co., Ltd.; FC-4430, 4432 manufactured by Sumitomo 3M Co., Ltd.; EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by Mitsubishi Materials Electronics & Chemical Co., Ltd.; and Ftergent 602A manufactured by NEOS Co., Ltd., etc.

[0151] Examples of nonionic surfactants include: polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristyl ether, polyoxyethylene octyl dodecyl ether, polyoxyethylene alkyl alkyl ether, polyoxyethylene phenyl distyrene phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyethylene alkyl alkenyl ether, polyoxyethylene nonyl phenyl ether, polyoxyethylene alkyl ether phosphate, sorbitol monolaurate, sorbitol monopalmitate, sorbitol monostearate, sorbitol distearate, sorbitol tristearate, etc. Sugar alcohol monooleate, dehydrated sorbitol trioleate, dehydrated sorbitol sesquioleate, polyoxyethylene dehydrated sorbitol monolaurate, polyoxyethylene dehydrated sorbitol monopalmitate, polyoxyethylene dehydrated sorbitol anhydride monostearate, polyoxyethylene dehydrated sorbitol tristearate, polyoxyethylene dehydrated sorbitol monooleate, polyoxyethylene dehydrated sorbitol triisostearate, tetraoleic polyoxyethylene sorbitol, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene cured castor oil, polyoxyethylene alkylamine, alkylalkanolamide, alkylimidazoline, etc.

[0152] Commercially available products include, for example: Emulgen manufactured by Kao Corporation, 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G -HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Rheodol SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amiet 102, 105, 105A, 302, 320, Aminon PK-02S, L-02, Homogenol L-95, and Adeka Pronik manufactured by ADEKA. Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, and Polyflow (meth)acrylic acid-based (co)polymers manufactured by Kyoei Chemical Co., Ltd., No. 75, No. 90, No. 95, etc.

[0153] Cationic surfactants include, for example, alkylamine salts or alkyl quaternary ammonium salts or ethylene oxide adducts of these, such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, cetyltrimethylammonium chloride, etc.

[0154] Commercially available products include, for example, Acetamin 24, Quartamin 24P, 60W, and 86P CONC manufactured by Kao Corporation.

[0155] Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfates, sodium dodecylbenzene sulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalene sulfonate, sodium alkyl diphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymers, polyoxyethylene alkyl ether phosphates, etc.

[0156] Commercially available products include, for example: Ftergent 100 and 150 manufactured by NEOS, and ADEKA HOPE YES-25, ADEKA COL TS-230E, PS-440E, EC-8600, etc. manufactured by ADEKA.

[0157] Examples of amphoteric surfactants include: alkyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, alkyl dimethylaminoacetic acid betaine, and other alkyl betaines; alkyl amine oxides such as lauryl dimethylamine oxide.

[0158] Commercially available products include: Amphitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​20N, etc., manufactured by Kao Corporation.

[0159] Leveling agent (M) can be used alone or in combination with two or more.

[0160] The leveling agent (M) content is preferably 0.001% to 2.0% by mass in 100% by mass of the non-volatile components of the photosensitive coloring composition, more preferably 0.005% to 1.0% by mass. By being within the range described, the balance between the coatability and adhesion of the photosensitive coloring composition is further improved.

[0161] <Storage Stabilizer> Photosensitive coloring compositions may contain storage stabilizers to stabilize the viscosity of the composition over time. Examples of storage stabilizers include: benzyltrimethyl chloride, diethylhydroxylamine and other quaternary ammonium chlorides, organic acids such as lactic acid and oxalic acid and their methyl ethers, tert-butylcatechol, tetraethylphosphine, tetraphenylphosphine and other organophosphines, phosphites, etc.

[0162] The content of storage stabilizer is preferably 0.1% to 10% by mass relative to 100 parts by mass of colorant (A).

[0163] <Adhesion Enhancer> The photosensitive coloring composition may contain an adhesion enhancer. This further improves the adhesion between the film and the substrate. Additionally, narrow patterns can be easily formed using photolithography. Examples of adhesion enhancers include silane coupling agents.

[0164] Examples of silane coupling agents include: vinyltrimethoxysilane, vinyltriethoxysilane, and other vinyl silanes; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyl Trimethoxysilanes and other (meth)acrylate silanes; 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, and other epoxysilanes; N-2-(aminoethyl)- 3-Aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3 -Aminopropyltrimethoxysilane hydrochloride and other aminosilanes; 3-mercaptopropylmethyldimethoxysilane, 3-mercaptopropyltrimethoxysilane and other mercapto compounds; p-styryltrimethoxysilane and other styryl compounds; 3-ureopropyltriethoxysilane and other ureo compounds; bis(triethoxysilylpropyl)tetrasulfide and other thioethers; 3-isocyanate propyltriethoxysilane and other isocyanates.

[0165] The content of the adhesion enhancer is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, relative to 100 parts by weight of the colorant (A). If it is contained in an appropriate amount, the photosensitivity of the photosensitive coloring composition is improved, the adhesion of the film is further improved, and the pattern resolution is also further improved.

[0166] <Solvent> Photosensitive coloring compositions may contain solvents. This makes viscosity adjustment of the photosensitive coloring composition easier, thus facilitating the formation of a smooth film. The solvent should be appropriately selected and contained in a suitable amount according to the intended use.

[0167] Examples of solvents 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 but not -O-, -CO- and -COO- in the molecule), aromatic hydrocarbon solvents, acetamide solvents, dimethyl sulfoxide, etc.

[0168] In terms of coatability and drying properties, the solvent is preferably an organic solvent with a boiling point of 120°C or higher and 180°C or lower at 1 atm. Among these, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc., are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc.

[0169] <Method for Manufacturing Photosensitive Coloring Composition> Photosensitive coloring composition can be manufactured, for example, by dispersing a colorant (A), a pigment derivative, and / or a dispersion resin to prepare a colorant dispersion; subsequently, the colorant dispersion, an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D) are formulated and mixed. Furthermore, the formulated materials and the timing of formulation are arbitrary. Additionally, the dispersion step can be performed multiple times.

[0170] The dispersion process may use dispersion devices such as kneaders, two-roll mills, three-roll mills, ball mills, horizontal sand mills, vertical sand mills, annular type bead mills, or grinders.

[0171] <Removal of Coarse Particles> In this specification, it is preferable to remove coarse particles during the colorant (A) dispersion stage or after the preparation of the photosensitive coloring composition. This removes foreign matter from the film, thus facilitating the formation of fine patterns. The removal is preferably performed by methods such as centrifugation, sintering filters, or membrane filters. This removes foreign matter such as coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, and even more preferably coarse particles of 0.5 μm or more. Thus, the photosensitive coloring composition preferably contains substantially no particles of 0.5 μm or more, and more preferably no particles of 0.3 μm or less.

[0172] <Water content in the photosensitive coloring composition> The photosensitive coloring composition of the present invention preferably contains 2% by mass or less of water. If the water content is within the range described above, the dispersion stability and sensitivity of the photosensitive coloring composition after storage over time are excellent. Furthermore, the water content is preferably 1.8% by mass or less, and more preferably 1.6% by mass or less.

[0173] There are no particular limitations on the method for controlling the water content, and known methods can be used. Examples include: a method for manufacturing a photosensitive coloring composition while blowing in dry inert gas; or a method for dehydrating the composition by placing it into a molecular sieve after manufacturing. Among these, the method of adjusting the water content while blowing in dry inert gas is preferred.

[0174] The water content can be determined by known methods such as the Karl-Fischer method.

[0175] <Color Filter> The color filter in this specification includes: a substrate (also referred to as a transparent substrate), and a filter segment formed of a photosensitive coloring composition. The filter segment (hereinafter also referred to as the filter segment) preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of colorant (A) used. Alternatively, the color filter may have a magenta filter segment, a cyan filter segment, and a yellow filter segment, which are complementary colors, instead of these filter segments. Furthermore, a reflective substrate may be used instead of a transparent substrate. Examples of transparent substrates include glass substrates. Examples of reflective substrates include substrates that use aluminum electrodes or metal thin films as reflective surfaces.

[0176] <Manufacturing Method of Color Filter> Regarding the color filter, it is preferable to first form a black matrix on a substrate, and then form the filter segment. Alternatively, the black matrix can be formed after pre-forming a thin-film transistor (TFT) on the substrate. Examples of black matrices include: multilayer films of chromium or chromium / chromium oxide, inorganic films such as titanium nitride, or resin films with dispersed opacifiers.

[0177] The filter segment can be formed by methods such as printing, electrodeposition, transfer printing, inkjet printing, and photolithography. In this specification, the most preferred method is photolithography.

[0178] The electrodeposition method utilizes a transparent conductive film formed on a transparent substrate, and through the electrophoresis of colloidal particles, electrodeposits various colored filter segments onto the transparent conductive film, thereby fabricating a color filter. Alternatively, the transfer method forms filter segments on the release surface of a release liner. Then, the filter segments are transferred onto a transparent substrate for fabrication.

[0179] Photolithography, for example, involves coating a photosensitive coloring composition containing a colorant of a certain hue onto a transparent substrate to form a film with a dry film thickness of approximately 0.2 μm to 5 μm. The obtained film (hereinafter referred to as the first film) is exposed (illuminated) through a mask with a predetermined pattern. Subsequently, it is developed by immersion in a solvent or alkaline developer or by spraying a developer such as a jet, removing uncured portions and obtaining the desired pattern. By similarly performing the above steps using a photosensitive coloring composition containing colorants of other hues, a color filter having filter segments of various colors can be manufactured. Furthermore, a second film (oxygen barrier film) can be formed on the first film before exposure using polyvinyl alcohol or water-soluble acrylic resin. As a result, the first film does not come into contact with oxygen, thus further improving exposure sensitivity. Additionally, the color filter can be heated to cure the uncured photopolymerizable compound in the filter segment.

[0180] Coating apparatus may include, for example, spray coating or spin coating, slot coating, roller coating, etc. A drying step may be performed during coating. Drying apparatus may include, for example, a hot air oven, an infrared heater, etc.

[0181] The developer solution may be an alkaline solution, for example, containing inorganic bases such as sodium carbonate and sodium hydroxide; or containing organic bases such as dimethylbenzylamine and triethanolamine. Additionally, an antifoaming agent or surfactant may be added to the developer solution.

[0182] The color filter of the present invention is bonded to an opposing substrate using a sealant. Liquid crystal is injected through an injection port provided in the sealing portion, and then the injection port is sealed. If necessary, a polarizing film or a retardation film is bonded to the outside of the substrate, thereby manufacturing a color liquid crystal display device. The color liquid crystal display device can be used for liquid crystal display modes that use color filters for colorization, such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically compensated bend (OCB).

[0183] In this specification, the color filter can be used not only in liquid crystal display devices, but also in solid-state photographic elements, organic electroluminescence (EL) display devices, quantum dot display devices, electronic paper, head-mounted displays, and other applications.

[0184] <Liquid Crystal Display Device> The image display device described in this specification includes a color filter. The image display device preferably further includes a light source. A liquid crystal display device will be described as an example of an image display device. The liquid crystal display device includes a color filter and a light source. Examples of light sources include cold cathode tubes (cold cathode fluorescent lamps, CCFLs) and white LEDs. In this invention, a white LED is preferred for its ability to reproduce a wide range of red areas. FIG1 is a schematic cross-sectional view of a liquid crystal display device 10 including the color filter of this invention. The device 10 shown in FIG1 includes a pair of spaced-apart and facing transparent substrates 11 and 21, between which a liquid crystal LC is encapsulated.

[0185] Liquid crystal LCs are aligned according to driving modes such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), and optically compensated birefringence (OCB). A TFT (thin-film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13, for example containing ITO, is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. In addition, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0186] On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0187] A transparent protective film (not shown) is formed on the color filter 22 as needed, and a transparent electrode layer 23 containing, for example, ITO is formed thereon, and an alignment layer 24 is provided by covering the transparent electrode layer 23.

[0188] In addition, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Furthermore, a backlight unit 30 is provided below the polarizing plate 15.

[0189] As a white LED light source, there are those with a fluorescent filter formed on the surface of a blue LED, or those containing a phosphor in the resin encapsulation of a blue LED, and preferably a white LED light source (LED 1) or a white LED light source (LED 2) having the following spectral characteristics: having a wavelength (λ3) where the luminous intensity becomes extremely large in the range of 430 nm to 485 nm, a wavelength (λ4) where the luminous intensity becomes extremely large in the range of 530 nm to 580 nm, and a wavelength (λ5) where the luminous intensity becomes extremely large in the range of 600 nm to 650 nm, and the ratio of the luminous intensity I3 at wavelength λ3 to the luminous intensity I4 at wavelength λ4 (I4 / I3) is 0.2 or more and 0.4 or less, and the ratio of the luminous intensity I3 at wavelength λ3 to the luminous intensity I5 at wavelength λ5 (I5 / I3) is 0.1 or more and 1.3 or less; the white LED light source (LED 2) has the following spectral characteristics: having a wavelength (λ3) where the luminous intensity becomes extremely large in the range of 430 nm to 485 nm, a wavelength (λ4) where the luminous intensity becomes extremely large in the range of 530 nm to 580 nm, and a wavelength (λ5) where the luminous intensity becomes extremely large in the range of 600 nm to 650 nm, and the ratio of the luminous intensity I3 at wavelength λ3 to the luminous intensity I5 at wavelength λ5 (I5 / I3) is 0.1 or more and 1.3 or less; the white LED light source (LED 2) has the following spectral characteristics: having a wavelength (λ3) where the luminous intensity becomes extremely large in the range of 430 nm to 485 nm, a wavelength (λ4) where the luminous intensity becomes extremely large in the range of 430 The light emission intensity has a wavelength (λ1) with the largest intensity in the range of nm and a peak wavelength (λ2) with the second largest intensity in the range of 530 nm to 580 nm. The ratio (I2 / I1) of the light emission intensity I1 at wavelength λ1 to the light emission intensity I2 at wavelength λ2 is 0.2 or more and 0.7 or less.

[0190] LED 1 For example, NSSW306D-HG-V1 (manufactured by Nichia Chemical Co., Ltd.) and NSSW304D-HG-V1 (manufactured by Nichia Chemical Co., Ltd.) can be listed.

[0191] Specifically, examples of LED 2 include NSSW440 (manufactured by Nichia Chemical Co., Ltd.) and NSSW304D (manufactured by Nichia Chemical Co., Ltd.). [Example]

[0192] Hereinafter, the present invention will be described by way of examples. However, the present invention is not limited to these examples. In addition, "parts" means "parts by mass" and "%" means "% by mass".

[0193] Before the examples, the calculation methods for determining the average molecular weight of the resin and the acid value of the resin will be explained.

[0194] (Average molecular weight of resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the resin were determined using gel permeation chromatography (GPC) equipped with a refractive index (RI) detector. An HLC-8220GPC (manufactured by Tosoh Corporation) was used as the apparatus, with two separation columns connected in series. Two “TSK-GEL SUPER HZM-N” columns were connected in the packing material of both columns. The determination was performed at an oven temperature of 40°C, using tetrahydrofuran (THF) solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent containing 1% by mass of the eluent, and injected in 20 μL. Molecular weights are converted from polystyrene values.

[0195] (Acid value of resin) Add 80 ml of acetone and 10 ml of water to 0.5 g to 1 g of resin solution and stir until homogeneous. Use a 0.1 mol / L potassium hydroxide (KOH) aqueous solution as the titrant and titrate using an automatic titration apparatus ("COM-555", manufactured by Hiranuma Sangyo Co., Ltd.) to determine the acid value (mgKOH / g). Furthermore, calculate the acid value per unit of non-volatile component of the resin based on the acid value of the resin solution and the concentration of non-volatile components in the resin solution.

[0196] (Amine value of alkaline resin dispersant (mgKOH / g)) The amine value of alkaline resin dispersant is obtained by converting the measured total amine value (mgKOH / g) into non-volatile components according to the method of American Society of Testing Material (ASTM) D 2074.

[0197] (Ammonium salt value (mgKOH / g)) The ammonium salt value is obtained by titrating with 0.1 N silver nitrate aqueous solution using 5% potassium chromate aqueous solution as indicator, and then converting it into the equivalent of potassium hydroxide. It represents the ammonium salt value of the non-volatile component.

[0198] <Manufacturing of Colorant (A)> (Micronized Red Pigment (A-1)) 100 parts of CI Pigment Red 254, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60°C for 6 hours. Next, the kneaded mixture was placed in warm water and heated to about 80°C while stirring with a high-speed mixer for 1 hour to form a slurry. The slurry was then filtered and washed with water to remove sodium chloride and diethylene glycol. After drying at 80°C for 24 hours, it was pulverized to obtain micronized red pigment (A-1).

[0199] (Micronized Red Pigment (A-2)) 100 parts of CI Pigment Red 177, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 60°C for 6 hours. Next, the kneaded mixture was placed in warm water and heated to about 80°C while stirring with a high-speed mixer for 1 hour to form a slurry. The slurry was then filtered and washed with water to remove sodium chloride and diethylene glycol. After drying at 80°C for 24 hours, it was pulverized to obtain micronized red pigment (A-2).

[0200] (Micronized Blue Pigment (A-3)) 100 parts of CI Pigment Blue 15:6, 1,000 parts of sodium chloride, and 100 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 50°C for 12 hours. The mixture was then added to 3,000 parts of warm water and stirred at a high speed for about 1 hour while heating to about 70°C to form a slurry. The slurry was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. After drying at 80°C for 24 hours, it was pulverized to obtain micronized blue pigment (A-3).

[0201] (Micronized Purple Pigment (A-4)) 100 parts of CI Pigment Violet 23, 1,200 parts of sodium chloride, and 100 parts of diethylene glycol were placed into a 1-gallon stainless steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 80°C for 6 hours. Next, the mixture was added to 8,000 parts of warm water and stirred at 80°C using a high-speed mixer for 2 hours to form a slurry. The slurry was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. After drying at 85°C for 24 hours, it was pulverized to obtain micronized purple pigment (A-4).

[0202] (Micronized Green Pigment (A-5)) 100 parts of CI Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed into a 1-gallon stainless steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 70°C for 6 hours. The mixture was then added to 3,000 parts of warm water and stirred at 70°C using a high-speed mixer for 1 hour to form a slurry. The slurry was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. After drying at 80°C for 24 hours, it was pulverized to obtain micronized green pigment (A-5).

[0203] (Micronized Green Pigment (A-6)) According to the example disclosed in Japanese Patent Application Publication No. 2017-111398, a green pigment (A-6) of the following chemical formula (12) was obtained. 100 parts of green pigment (A-6), 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed into a 1-gallon stainless steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 70°C for 6 hours. The mixture was then added to 3,000 parts of warm water and stirred at 70°C using a high-speed mixer for 1 hour to form a slurry. The slurry was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. After drying at 80°C for 24 hours, it was pulverized to obtain micronized green pigment (A-6). Chemical formula (12) [Chemical 9]

[0204] (Micronized Yellow Pigment (A-7)) 100 parts of CI Pigment Yellow 150, 700 parts of sodium chloride, and 180 parts of diethylene glycol were placed into a 1-gallon stainless steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 80°C for 6 hours. The mixture was then added to 2,000 parts of warm water and stirred at 80°C using a high-speed mixer for 1 hour to form a slurry. The slurry was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. After drying at 80°C for 24 hours, it was pulverized to obtain micronized yellow pigment (A-7).

[0205] (Micronized Yellow Pigment (A-8)) 100 parts of CI Pigment Yellow 138, 800 parts of pulverized sodium chloride, and 100 parts of diethylene glycol were placed into a 1-gallon stainless steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 70°C for 12 hours. The mixture was then added to 3000 parts of warm water and stirred at a high speed for about 1 hour while heating to about 70°C to form a slurry. The slurry was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. After drying at 80°C for 24 hours, it was pulverized to obtain micronized yellow pigment (A-8).

[0206] (Micronized Yellow Pigment (A-9)) 100 parts of CI Pigment Yellow 185 (Palitol Yellow D1155 manufactured by BASF Japan), 700 parts of pulverized sodium chloride, and 180 parts of diethylene glycol were placed into a 1-gallon stainless steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 80°C for 6 hours. Next, the mixture was placed into 8 liters of warm water and stirred at 80°C using a high-speed mixer for 2 hours to form a slurry. The slurry was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. After drying at 85°C for 24 hours, it was pulverized to obtain micronized yellow pigment (A-9).

[0207] (Micronized Yellow Pigment (A-10)) Following the example disclosed in Japanese Patent Application Publication No. 2012-226110, a yellow pigment (A-10) of the following chemical formula (13) was obtained. 100 parts of yellow pigment (A-10), 700 parts of pulverized sodium chloride, and 180 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded at 80°C for 6 hours. Next, the mixture was placed in 8 liters of warm water and stirred for 2 hours using a high-speed mixer while heating to 80°C to form a slurry. The slurry was repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. It was then dried at 85°C for 24 hours and pulverized to obtain a micronized yellow pigment (A-10). Chemical Formula (13) [Chemical Formula 10]

[0208] The average primary particle size of the micronized pigment is in the range of 5 nm to 120 nm.

[0209] (Dye (A-11)) A salt-forming compound, namely dye (A-11), comprising C1 Acid Red 52 and resin 1 having cationic groups on the side chain, is prepared in the following order. 67.3 parts of methyl ethyl ketone are added to a four-necked separable flask including a thermometer, stirrer, distillation tube, and cooler, and the mixture is heated to 75°C under a nitrogen atmosphere. Meanwhile, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2'-azobis(2,4-dimethylpentanonitrile), and 25.1 parts of methyl ethyl ketone are homogenized and then loaded into a dropping funnel. The dropping funnel is then placed in the four-necked separable flask, and the addition is carried out over 2 hours. Two hours after the addition was completed, the polymerization yield was confirmed to be over 98% based on the non-volatile components, with a weight average molecular weight (Mw) of 6,830, and the mixture was cooled to 50°C. 3.2 parts of chloromethane and 22.0 parts of ethanol were added, and the mixture was reacted at 50°C for 2 hours, then heated to 80°C for 1 hour and reacted for another 2 hours. This yielded resin 1 with a resin composition of 47% by mass and cationic groups on the ammonium side chains. The ammonium salt value of the obtained resin was 34 mgKOH / g. Next, 30 parts of resin 1 with cationic groups on the side chains (based on non-volatile components) were added to 2,000 parts of water, and after thorough mixing, the mixture was heated to 60°C. Meanwhile, an aqueous solution was prepared by dissolving 10 parts of CI Acid Red 52 in 90 parts of water, and this solution was added dropwise to the resin solution. After the addition, the mixture was stirred at 60°C for 120 minutes to allow for complete reaction. To confirm the endpoint of the reaction, the reaction solution was added dropwise to filter paper, and the endpoint was determined when the exudation stopped, indicating that a salt-forming compound had been obtained. After stirring and cooling to room temperature, the mixture was filtered by suction and washed with water. The remaining salt-forming compound on the filter paper was then dried using a dryer to remove moisture, yielding 32 parts of a salt-forming compound of CI Acid Red 52 and resin 1 with cationic groups on the side chains, i.e., dye (A-11). At this point, the content of the component derived from CI Acid Red 52 in dye (A-11) was 25% by mass.

[0210] <Preparation of Alkali-Soluble Resin (B)> (Alkali-Soluble Resin (B1-1) Solution) 270.0 parts of propylene glycol monomethyl ether acetate (hereinafter, also known as PGMAc) were placed in a reaction vessel equipped with a thermometer, cooling pipe, nitrogen gas inlet pipe, and stirring device on a separable four-necked flask. While injecting nitrogen gas into the vessel, the mixture was heated to 120°C. At the same temperature, a mixture of 80.0 parts of glycidyl methacrylate (hereinafter, GMA), 75.0 parts of dicyclopentyl methacrylate (hereinafter, DCPMA), 29.0 parts of styrene, and 19.0 parts of tert-butyl peroxide-2-ethylhexanoate as a polymerization initiator and PGMAc was added dropwise over 2.5 hours via a dropper. After the addition was complete, the mixture was stirred at 120°C for another 2 hours to obtain the precursor. Subsequently, the flask was purged with air, and 40.6 parts of acrylic acid (hereinafter, AA) as a modifying compound, 0.6 parts of triphenylphosphine as a catalyst, and 0.2 parts of methylhydroquinone were added. The mixture was reacted at 110°C for 10 hours. This yielded a monomer unit (hereinafter, GMA+AA) formed by reacting the epoxy group of GMA with the carboxyl group of AA, introducing a monomer unit containing a polymerizable unsaturated group. Next, 93.0 parts of succinic anhydride (hereinafter, SHA) as a modifying compound were added, and the mixture was reacted at 110°C for 4 hours. This caused a portion of the hydroxyl groups of GMA+AA to react with SHA. Subsequently, PGMAc was added in such a way that the non-volatile component was 20% by mass to prepare an alkali-soluble resin (B1-1) solution. The alkali-soluble resin (B1-1) had an acid value of 79 mgKOH / g and a weight average molecular weight of 6,000.

[0211] (Alkali-soluble resin (B1-2) ~ alkali-soluble resin (B1-3) solution) Alkali-soluble resin (B1-2) ~ alkali-soluble resin (B1-3) were synthesized using the same method as alkali-soluble resin (B1-1) by changing the type and amount of the formulation in the manner described in Table 1, and PGMAc was added, with the non-volatile component set at 20% by mass.

[0212] [Table 1] Table 1 (B1-1) (B1-2) (B1-3) Composition ratio (Moll%) Containing alicyclic hydrocarbons Monomer unit methacrylic acid Dicyclopentyl ester 30 30 5 Containing polymeric unsaturated groups Monomer unit GMA+AA twenty one twenty one MAA+GMA 60 GMA+AA+THPA 39 GMA+AA+SHA 39 Other monomers unit benzyl methacrylate 10 styrene 10 10 methacrylic acid 25 acid value 79 79 110 Weight-average molecular weight (Mw) 6000 9000 16700

[0213] In Table 1, MAA+GMA represents a monomer unit containing a polymerizable unsaturated group formed by adding an epoxy group of GMA to the carboxyl group of the precursor derived from methacrylic acid (hereinafter, MAA). GMA+AA+THPA represents a monomer unit containing a polymerizable unsaturated group formed by reacting a portion of the hydroxyl group at the reaction site of GMA+AA with tetrahydrophthalic anhydride (hereinafter, THPA).

[0214] (Alkali-soluble resin (B2-1) solution) 196 parts of cyclohexanone were added to a reaction vessel equipped with a thermometer, cooling pipe, nitrogen gas inlet pipe, dropper, and stirring device on a separable four-necked flask. The temperature was raised to 80°C, and the reaction vessel was purged with nitrogen. Over a period of 2 hours, a mixture of 25.1 parts of benzyl methacrylate, 23.0 parts of n-butyl methacrylate, 14.3 parts of 2-hydroxyethyl methacrylate, 13.4 parts of methacrylic acid, 24.1 parts of p-cumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise through the dropper. After the addition was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately two portions of the resin solution were sampled and dried at 180°C for 20 minutes. The non-volatile components were then determined. PGMAc was added to the previously synthesized resin solution at a non-volatile component concentration of 20% by mass to prepare an alkali-soluble resin solution (B2-1). The acid value was 87 mgKOH / g, and the weight-average molecular weight was 25,000.

[0215] <Preparation of Polymerizable Compound (C)> (Aliphatic Aminocarbamate (Meth)acrylate (C1-3)) 400 parts of dipentaerythritol pentaacrylate, 100 parts of propylene glycol monomethyl ether acetate, and 0.5 parts of N,N-dimethylbenzylamine were added to a five-necked flask containing a stirrer, reflux condenser, nitrogen inlet, thermometer, and dropper. The mixture was heated to 70°C and, over a period of 2 hours, a mixture of 64 parts of hexamethylene diisocyanate and 64 parts of propylene glycol monomethyl ether acetate was added dropwise through the dropper. After the addition, the mixture was reacted at 50°C–70°C for 8 hours. The disappearance of the isocyanate absorption at 2180 cm⁻¹ was confirmed by infrared spectroscopy (IR). The solvent was removed by distillation to obtain aliphatic aminocarbamate acrylate (C1-3) with a polymerizable unsaturated base number of 10.

[0216] (Polymerizable compound with acid groups (C3-2)) 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine were added to a five-necked flask including a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropper. The temperature was raised to 70°C, and a mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise over 2 hours via the dropper. After the addition, the reaction was carried out at 50°C–70°C for 8 hours, and the disappearance of isocyanate absorption at 2180 cm⁻¹ was confirmed by IR. Subsequently, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were added, and the reaction was carried out at 50°C–60°C for 6 hours. The solvent was removed by distillation to obtain a polymerizable compound with acid groups (C3-2).

[0217] <Preparation of Dispersion Resin (G)> (Dispersion Resin (G-1) Solution) 10 parts methacrylic acid, 100 parts methyl methacrylate, 70 parts isobutyl methacrylate, 20 parts benzyl methacrylate, and 50 parts PGMAc were added to a reaction vessel including a gas inlet tube, thermometer, condenser, and stirrer, and the vessel was purged with nitrogen gas. The reaction vessel was heated and stirred to 50°C, and 12 parts 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and a solution prepared by adding 0.1 parts 2,2'-azobisisobutyronitrile to 90 parts PGMAc was added while reacting for 7 hours. The reaction was confirmed to have reached 95% by measuring the non-volatile components. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 100°C for 7 hours. The reaction was terminated after confirming that more than 98% of the anhydride had undergone half-esterification by acid value determination. PGMac was added to dilute the solution to a non-volatile content of 30%, resulting in a dispersion resin (G-1) solution with an acid value of 70 mgKOH / g and a weight average molecular weight of 8,500.

[0218] (Dispersion Resin (G-2) Solution) 108 parts of 1-thiopropanetriol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged into a reaction vessel including a gas inlet tube, thermometer, condenser, and stirrer. After purging with nitrogen gas, the reaction was carried out at 120°C for 5 hours (first step). The acid value was measured, confirming that over 95% of the anhydride underwent half-esterification. Next, the following were added to the reaction vessel: 160 parts of the compound obtained in the first step, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of tert-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc. The reaction vessel was heated to 80°C, and 1.2 parts of 2,2'-azobis(2,4-dimethylpentanonitrile) were added. The reaction was carried out for 12 hours (second step). The reaction was confirmed to have reached 95% by non-volatile component determination. Finally, 500 parts of a PGMAc dilution solution containing 50% non-volatile components of the compound obtained in step two, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were added, and the reaction was carried out until the disappearance of the peak at 2270 cm⁻¹ based on the isocyanate group was confirmed by IR spectroscopy (step three). After confirming the disappearance of the peak, the reaction solution was cooled, and the non-volatile components were adjusted using PGMAc to obtain a dispersion resin (G-2) solution with 30% non-volatile components. The obtained dispersion resin (G-2) had an acid value of 68 mgKOH / g, an unsaturated double bond equivalent of 1,593, and a weight average molecular weight of 13,000.

[0219] (Dispersion Resin (G-3) Solution) 3 parts trimellitic anhydride, 1 part 3-mercapto-1,2-propanediol, 50 parts methoxypropyl acetate, and 0.1 parts dimethylbenzylamine were added to a reaction vessel equipped with a gas inlet pipe, condenser, stirring blades, and thermometer. After purging with nitrogen gas, the reaction vessel was heated to 120°C and reacted for 4 hours, followed by a reaction at 80°C for 2 hours. Then, 30 parts tert-butyl acrylate, 20 parts ETERNACOLL OXMA (methyl methacrylate (3-ethyl-3-oxetanebutyl) acrylate, manufactured by Ube Industries, Ltd.), 5 parts methacrylic acid, 40 parts ethyl acrylate, and 10 parts methoxypropyl acetate were added. While maintaining the reaction vessel at 80°C, 0.2 parts 2,2'-azobisisobutyronitrile were added in 15 portions every 30 minutes. One hour after the final addition, the non-volatile components were measured, confirming that 95% of the monomer had reacted. The reaction was then completed by dilution with methoxypropyl acetate and cooling. A dispersion resin (G-3) with 30% non-volatile components, an acid value of 51 mgKOH / g per unit of non-volatile component, and a weight-average molecular weight (Mw) of 24,000 was obtained.

[0220] (Dispersion Resin (G-4) Solution) 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were added to a reaction apparatus equipped with a gas inlet pipe, condenser, stirring blades, and thermometer. The system was stirred at 50°C for 1 hour while passing nitrogen gas to purge the system. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were added. The mixture was heated to 110°C under a nitrogen flow to initiate the polymerization of the first block (B-block). After 4 hours of polymerization, a sample of the polymerization solution was taken for non-volatile component determination. Based on the non-volatile component conversion, the polymerization conversion rate was confirmed to be above 98%. Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidine methacrylate (manufactured by Hitachi Chemical Co., Ltd., not Fancryl FA-711MM) as the second block (A block) monomer were added to the reaction apparatus. The reaction was continued by stirring at 110°C under a nitrogen atmosphere. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidine methacrylate, a sample of the polymerization solution was taken for non-volatile content determination. Based on the non-volatile content, the polymerization conversion to the second block (A block) was confirmed to be over 98%, and the reaction solution was cooled to room temperature to stop the polymerization. PGMAc was added to dilute the non-volatile content to 30%, thereby obtaining a dispersion resin (G-4) solution with an amine value of 57 mgKOH / g per unit of non-volatile content and a number average molecular weight of 4,500 (Mn).

[0221] (Dispersion Resin (G-5) Solution) In a 500 mL round-bottom four-necked separable flask including a cooling tube, a funnel for adding, a nitrogen inlet, a stirrer, and a digital thermometer, 250 parts by weight of tetrahydrofuran (THF) and 5.81 parts by weight of dimethyl ketene methyltrimethylsilyl acetal as an initiator were added via the funnel, followed by thorough nitrogen purging. 0.5 parts by weight of a 1 mole / L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected using a syringe. Using the funnel, 19.7 parts by weight of 2-hydroxyethyl methacrylate, 7.5 parts by weight of 2-ethylhexyl methacrylate, 12.9 parts by weight of n-butyl methacrylate, 10.7 parts by weight of benzyl methacrylate, and 30.9 parts by weight of methyl methacrylate were added dropwise over 60 minutes as solvent-friendly block monomers. The temperature was maintained below 40°C by cooling the flask with an ice bath. One hour later, 18.3 parts by mass of dimethylaminopropyl methacrylamide, a block monomer with color material adsorption function, was added dropwise over a period of 20 minutes. After another hour of reaction, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was redeprecipitated in hexane and purified by filtration and vacuum drying. Subsequently, 15.0 parts by mass of the obtained block copolymer was dissolved in 35 parts by mass of PGMAc in a 100 mL round-bottom flask, and 1.1 parts by mass of phenylphosphonic acid (0.5 molar equivalents relative to dimethylaminopropyl methacrylamide), a salt-forming component, was added. The mixture was stirred at 30°C for 20 hours, and PGMAc was added to adjust the concentration to obtain a dispersion resin (G-5) solution with 30% non-volatile components.

[0222] <Preparation of Dispersion> (Dispersion 1) Dispersion 1 was prepared by dispersing 0.5 mm diameter zirconia beads in an Eiger mill (M-250 MKII mini model manufactured by Eiger Japan) for 3 hours, followed by filtration using a 1.0 μm pore size filter. The organic solvent (P-1) was PGMAc. Micronized blue pigment (A-3): 9.05 parts by mass; Micronized purple pigment (A-4): 0.31 parts by mass; Dye (A-11): 4.16 parts by mass; Pigment derivative (F-1): 1.04 parts by mass; Dispersion resin (G-1) solution: 3.47 parts by mass; Alkali-soluble resin (B2-1) solution: 10.0 parts by mass; Organic solvent (P-1): 71.97 parts by mass.

[0223] Pigment derivative (F-1): A compound with the following structure [Chemical 11] where n is an integer from 1 to 4.

[0224] Except for changing the raw materials and quantities recorded in Table 2, dispersions 2 to 9 are prepared in the same manner as dispersion 1.

[0225] [Table 2] Table 2 Dispersion 1 Dispersion 2 Dispersion 3 Dispersion 4 Dispersion 5 Dispersion 6 Dispersion 7 Dispersion 8 Dispersion 9 Colorant (A) (A-1) 12.32 (A-2) 11.32 (A-3) 9.05 (A-4) 0.31 (A-5) 14.00 (A-6) 9.00 (A-7) 12.25 (A-8) 8.055 (A-9) 10.00 (A-10) 10.20 (A-11) 4.16 Pigment derivatives (F) (F-1) 1.04 (F-2) 0.945 4.00 1.80 (F-3) 0.84 (F-4) 1.75 0.84 (F-5) 2.16 Dispersion resin (G) solution (G-1) 3.47 6.00 4.00 7.00 6.57 10.00 12.00 10.00 11.76 (G-2) 2.50 0.83 6.33 10.00 10.00 (G-3) 1.00 1.00 (G-4) 7.50 6.77 (G-5) 10.50 10.00 8.00 Alkali-soluble resin (B) solution (B2-1) 10.00 10.00 10.00 10.00 10.00 10.00 Organic solvents (P) (P-1) 71.97 66.00 67.67 62.67 67.67 56.00 58.00 66.00 64.77

[0226] Pigment derivatives (F-2) in Table 2: The following structures [Chemical 12]

[0227] The pigment derivatives in Table 2 (F-3): The following structures [Chemical 13] are used, where Me represents methyl.

[0228] The pigment derivatives in Table 2 (F-4): The following structure [Chemical 14] wherein Et represents ethyl.

[0229] Pigment derivatives in Table 2 (F-5): The following structures [Chemical 15]

[0230] <Preparation of Photosensitive Coloring Composition> [Example 1] (Photosensitive Coloring Composition 1) The following raw materials were mixed and stirred, and filtered through a filter with a pore size of 1.0 μm to obtain photosensitive coloring composition 1. Dispersion 3: 31.74 parts by mass Dispersion 5: 27.44 parts by mass Alkali-soluble resin (B1-1) solution: 2.90 parts by mass Polymerizing compound (C1-1): 2.12 parts by mass Polymerizing compound (C2-1): 1.20 parts by mass Polymerizing compound (C4-1): 1.70 parts by mass Oxime ester photopolymerization initiator (D2b-1): 0.44 parts by mass Thermosetting compound (H1-1): 0.08 parts by mass Polymerization inhibitor (J): 0.0015 parts by mass Leveling agent (M): 0.50 parts by mass Organic solvent (P): 31.89 parts by mass

[0231] [Examples 2 to 30, Comparative Examples 1 to 2] Except that the photosensitive coloring composition 1 of Example 1 was changed to the raw materials and amounts described in Tables 3-1 to 3-4, the photosensitive coloring compositions of Examples 2 to 30 and Comparative Examples 1 to 2 were prepared in the same manner as in Example 1.

[0232] [Table 3-1] Table 3-1 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Colorant (A) Dispersion 1 Dispersion 2 Dispersion 3 31.74 31.74 31.74 31.74 31.74 31.74 31.74 31.74 31.74 31.74 31.74 Dispersion 4 Dispersion 5 27.44 27.44 27.44 27.44 27.44 27.44 27.44 27.44 27.44 27.44 27.44 Dispersion 6 Dispersion 7 Dispersion 8 Dispersion 9 Alkali-soluble resin (B) (B1-1) 2.90 2.90 2.90 2.90 2.90 2.90 2.90 2.90 2.90 2.90 2.90 (B1-2) (B1-3) Polymerizable compounds (C) (C1-1) 2.12 2.12 2.12 2.12 2.12 2.12 2.12 2.12 2.12 (C1-2) 2.12 (C1-3) 2.12 (C1-4) (C1-5) (C1-6) (C2-1) 1.20 1.20 1.20 2.25 1.20 1.20 1.20 (C2-2) 1.20 (C2-3) 1.20 (C2-4) 1.20 (C3-1) 1.70 (C4-1) 1.70 1.70 1.70 2.90 0.65 1.70 1.70 1.70 1.70 1.70 Photopolymerization initiator (D) (D1-1) (D2b-1) 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 (D2b-2) 0.44 (D2b-3) 0.44 (D2a-1) (D2a-2) (D3-1) Senser (E) (E1-1) Thermosetting compounds (H) (H1-1) 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 Polymerization inhibitors (J) 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 Leveling agent (M) 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Organic solvents (P) 31.89 31.89 31.89 31.89 31.89 31.89 31.89 31.89 31.89 31.89 31.89

[0233] [Table 3-2] Table 3-2 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Colorant (A) Dispersion 1 21.50 Dispersion 2 30.74 31.20 Dispersion 3 32.00 31.50 31.00 31.74 31.74 31.74 31.74 Dispersion 4 11.57 6.85 Dispersion 5 15.52 27.44 27.44 27.44 27.44 Dispersion 6 8.68 Dispersion 7 14.25 Dispersion 8 22.63 Dispersion 9 25.48 Alkali-soluble resin (B) (B1-1) 4.91 11.71 14.11 9.78 9.24 28.36 0.93 2.90 2.90 (B1-2) 2.90 (B1-3) 2.90 Polymerizable compounds (C) (C1-1) 2.12 2.12 2.12 2.12 2.12 2.12 2.12 2.12 2.12 (C1-2) (C1-3) (C1-4) 2.12 (C1-5) 2.12 (C1-6) (C2-1) 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 1.20 (C4-1) 1.70 1.70 1.70 1.70 1.70 1.70 1.35 1.70 1.70 1.70 1.70 Photopolymerization initiator (D) (D1-1) (D2b-1) 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 0.44 (D2b-2) (D2b-3) (D2a-1) (D2a-2) (D3-1) Sensitive agent (E1-1) Thermosetting compounds (H) (H1-1) 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 Polymerization inhibitors (J) 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 Leveling agent (M) 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Organic solvents (P) 42.80 38.68 39.68 38.93 46.68 44.10 45.28 31.89 31.89 31.89 31.89

[0234] [Table 3-3] Table 3-3 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Comparative Example 1 Comparative Example 2 Colorant (A) Dispersion 1 Dispersion 2 Dispersion 3 31.74 31.74 31.74 31.74 31.74 31.74 31.74 31.74 31.74 31.74 31.74 Dispersion 4 Dispersion 5 27.44 27.44 27.44 27.44 27.44 27.44 27.44 27.44 27.44 27.44 27.44 Dispersion 6 Dispersion 7 Dispersion 8 Dispersion 9 Alkali-soluble resin (B) (B1-1) 2.90 2.90 2.90 2.90 2.90 2.90 2.90 2.90 2.90 2.90 2.90 (B1-2) (B1-3) Polymerizable compounds (C) (C1-1) 2.12 2.12 2.12 2.12 2.12 2.12 1.70 3.00 2.12 (C1-2) (C1-3) (C1-4) (C1-5) (C1-6) 2.12 (C2-1) 1.20 1.20 1.20 1.20 1.20 1.20 0.30 3.32 1.20 1.20 1.20 (C4-1) 1.70 1.64 1.64 1.54 1.54 1.54 2.60 0.82 1.70 1.70 Photopolymerization initiator (D) (D1-1) 0.20 0.44 (D2b-1) 0.44 0.40 0.40 0.40 0.40 0.40 0.44 0.44 0.44 0.44 (D2b-2) (D2b-3) (D2a-1) 0.10 (D2a-2) 0.10 (D3-1) 0.20 sensitizer (E1-1) 0.20 Thermosetting compounds (H) (H1-1) 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 0.08 Polymerization inhibitors (J) 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 0.0015 Leveling agent (M) 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 0.50 Organic solvents (P) 31.89 31.89 31.89 31.89 31.89 31.89 31.89 31.89 31.89 31.89 31.89

[0235] The materials in the table are as follows.

[0236] [Polymerizable compound (C)] (Aminocarbamate acrylate (C1)) C1-1: UA-306H (manufactured by Kyoeisha Chemical Co., Ltd.) A polyfunctional aminocarbamate (meth) acrylate (aliphatic, 6-functional) as a product of the reaction of pentaerythritol triacrylate and hexamethylene diisocyanate C1-2: UA-306I (manufactured by Kyoeisha Chemical Co., Ltd.) A polyfunctional aminocarbamate (meth) acrylate (aliphatic, 6-functional) as a product of the reaction of pentaerythritol triacrylate and isophorone diisocyanate C1-3: The compound synthesized by the following method was loaded into a five-necked reaction vessel with a capacity of 1 liter, containing 284 parts of glycidyl methacrylate, 144 parts of acrylic acid, 0.4 parts of methoxyphenol, and 5 parts of triphenylphosphine, and reacted at 80°C for 12 hours to obtain 2-hydroxy-3-acrylic propyl methacrylate. Then, 168 parts of hexamethylene diisocyanate were added to the mixture, and the reaction was carried out at 60°C for 8 hours to obtain a product containing a polyfunctional aminocarbamate acrylate (C1-3) with (meth)acrylic groups. The polyfunctional aminocarbamate acrylate (C1-3) accounted for 100% by weight in the product. Furthermore, IR analysis confirmed the absence of isocyanate groups in the reaction product. (Aliphatic, 4-functional) C1-4: The compound synthesized by the following method was added to a 1-liter five-necked reaction vessel containing 142 parts of glycidyl methacrylate, 77 parts of acrylic acid, 0.2 parts of methoxyphenol, and 3 parts of triphenylphosphine, and reacted at 80°C for 12 hours to obtain 2-hydroxy-3-acrylic propyl methacrylate. Furthermore, 490 parts of a trimethylolpropane hexamethylene diisocyanate adduct [Coronate HL (manufactured by Nippon Polyurethane Co., Ltd.)] were added to the adduct and reacted at 60°C for 8 hours to obtain a product containing a polyfunctional aminoform acrylate (C1-4) with (meth)acrylic groups. The polyfunctional aminoform acrylate (C1-4) accounted for 100% by weight in the product. Furthermore, IR analysis confirmed the absence of isocyanate groups in the reaction product. (Aliphatic, 4-functional) C1-5: The compound synthesized by the following method was added to a 1-liter five-necked reaction vessel containing 623 parts of dipentaerythritol hexaacrylate (manufactured by Toa Synthetic Co., Ltd.) and 44 parts of hexamethylene diisocyanate, and reacted at 60°C for 8 hours to obtain a product containing a polyfunctional aminoform acrylate (C1-5) with (meth)acrylic groups. In the product, polyfunctional aminocarbamate acrylates (C1-5) account for 45% by weight, with the remainder consisting of other photopolymerizable monomers. Furthermore, IR analysis confirmed the absence of isocyanate groups in the reaction product.(Aliphatic, 10-functional) C1-6: The compound synthesized by the following method was charged into a five-necked flask containing a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube. 400 parts of dipentaerythritol pentaacrylate, 100 parts of propylene glycol monomethyl ether acetate, and 0.5 parts of N,N-dimethylbenzylamine were added. The temperature was raised to 70°C, and a mixture of 66 parts of toluene diisocyanate and 66 parts of propylene glycol monomethyl ether acetate was added dropwise over 2 hours via the dropping tube. After the addition, the reaction was carried out at 50°C–70°C for 8 hours, and the disappearance of isocyanate absorption at 2,180 cm⁻¹ was confirmed by IR. Subsequently, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were added, and the reaction was carried out at 50°C–60°C for 6 hours. A polymeric compound (C1-6) with an average number of unsaturated groups of 9 and containing acidic groups and carbamate bonds was prepared by adjusting the amount of non-volatile components to 50% by mass. (Aromatic, 9-functional).

[0237] (Polymerizable compounds with a viscosity of 800 mPa·S or less at 25°C (C2)) The number of functional groups of the polymerizable unsaturated group and the viscosity at 25°C are recorded in parentheses. C2-1: Trimethylolpropane triacrylate; M-309 (manufactured by Toa Synthetic Co., Ltd.; 3-functional, 60 mPa·S-150 mPa·S) C2-2: Trimethylolpropane PO modified triacrylate; M-310 (manufactured by Toa Synthetic Co., Ltd.; 3-functional, 60 mPa·S-110 mPa·S) In addition, PO is propylene oxide. C2-3: Pentaerythritol triacrylate and pentaerythritol pentaacrylate; M-450 (manufactured by Toa Synthetic Co., Ltd.; 4 functional, 400 mPa·S-650 mPa·S) C2-4: Tricyclodecanedimethyl diacrylate; A-DCP (manufactured by Shin-Nakamura Chemical Co., Ltd.; 2 functional, 135 mPa·S)

[0238] (Polymerizable compound with acid group (C3)) C3-1: Aronix M-520 (manufactured by Dong-A Synthetic Co., Ltd., polyacid-modified acrylic oligomer, acid group: carboxyl group)

[0239] (Other polymeric compounds (C4)) C4-1: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate)

[0240] [Photopolymerization initiator (D)] [A compound containing two oxime ester groups in one molecule (D2b)] D2b-1: Compound of chemical formula (2) D2b-2: Compound of chemical formula (3) D2b-3: Compound of chemical formula (4)

[0241] 〔A compound containing one oxime ester group in one molecule (D2a)〕 D2a-1: TRONLY TR-PBG-3057 (manufactured by Changzhou TRONLY New Materials Co., Ltd., a compound containing one oxime ester group in one molecule) D2a-2: The compound of the chemical formula (6)

[0242] (Photopolymerization initiator with a fluorene skeleton and without an oxime ester group (D1)) D1-1: Compound of the chemical formula (9)

[0243] (Other photopolymerization initiators (D3)) D3-1: Omnirad 379EG (manufactured by IGM Resins, acetophenone compound)

[0244] [Senser (E)] (Thioxanthone compound (E1)) E1-1: 2,4-Diethylthioxanthone

[0245] [Thermosetting compound] (Epoxy compound (H1)) H1-1: EHPE-3150 (manufactured by Daicel)

[0246] [Polymerization Inhibitor (J)] J-1: 4-methylcatechol J-2: methylhydroquinone J-3: tert-butylhydroquinone The above are mixed in the same amount as (J-1) to (J-3) to obtain the polymerization inhibitor (J).

[0247] [Leveling Agent (M)] M-1: BYK-330 (manufactured by BYK-Chemie) M-2: Megafac F-551 (manufactured by DIC) Mix 1 part of each of (M-1) and (M-2) and dissolve them in 98 parts of PGMac. The resulting mixed solution is used as leveling agent (M).

[0248] [Organic solvent (P)] P-1: 30 parts of propylene glycol monomethyl ether acetate P-2: 30 parts of cyclohexanone P-3: 10 parts of ethyl 3-ethoxypropionate P-4: 10 parts of propylene glycol monomethyl ether P-5: 10 parts of cyclohexanol acetate P-6: 10 parts of dipropylene glycol methyl ether acetate, and (P-1) to (P-6) are mixed in the above-mentioned mass parts to form an organic solvent (P).

[0249] <Evaluation of the photosensitive coloring composition> The obtained photosensitive coloring composition was evaluated for heat resistance, bulk density, linewidth sensitivity, and wrinkle resistance using the following methods. The evaluation results are shown in Table 4.

[0250] [Heat Resistance Evaluation] The obtained photosensitive coloring composition was spin-coated onto a glass substrate (Eagle 2000 manufactured by Corning) with a length of 100 mm × width of 100 mm and a thickness of 0.7 mm to a dried film thickness of 2.5 μm, and dried using a vacuum dryer. Subsequently, it was exposed to a high-pressure mercury lamp at an illuminance of 30 mW / cm2 and an exposure dose of 25 mJ / cm2. Afterward, it was developed by jet spraying with a sodium carbonate aqueous solution at 23°C for 40 seconds, washed with deionized water and air-dried, and heated in a clean oven at 230°C for 30 minutes. The colorimetric properties ([L*(1), a*(1), b*(1)]) of the obtained coating under C light source were measured using a microspectrophotometer (OSP-SP100 manufactured by Olympus Optics). Subsequently, as an evaluation of heat resistance, the chromaticity ([L*(2), a*(2), b*(2)]) under light source C was measured after heating at 230°C for 1 hour. The color difference ΔEab* was calculated using the following formula. The evaluation criteria are as follows, with 3 or higher considered practical. ΔEab* = ((L*(2) - L*(1))² + (a*(2) - a*(1))² + (b*(2) - b*(1))²)¹ / ² 5: ΔEab* is less than 1 4: ΔEab* is 1 or higher and less than 2 3: ΔEab* is 2 or higher and less than 3 2: ΔEab* is 3 or higher and less than 5 1: ΔEab* is 5 or higher

[0251] [Evaluation of Stacking Ratio] The stacking ratio was used to evaluate the height control of the stacked optical spacers. The obtained photosensitive coloring composition was spin-coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) with a black matrix, to a dry film thickness of 2.5 μm. The substrate was then dried using a vacuum dryer. Subsequently, exposure was performed using a high-pressure mercury lamp at an illuminance of 30 mW / cm² and an exposure dose of 25 mJ / cm² using a photomask including a pixel mask and a photomask for the stacked optical spacers. Afterward, the substrate was developed by jet spray with a sodium carbonate aqueous solution at 23°C for 40 seconds, rinsed with deionized water, air-dried, and then heated in a clean oven at 230°C for 30 minutes. Next, the film thickness (a) of the pixels shown in the cross-sectional view (Figure 2) of the color filter and the film thickness (b) of the stacked portion on the black matrix were measured using a contact thickness gauge, and the stacking ratio ((b÷a)×100) was calculated. The results are shown in Table 4. 3 and above are practical. 5: Stacking ratio 75% and above but less than 80% 4: Stacking ratio 80% and above but less than 82.5% 3: Stacking ratio 82.5% and above but less than 85% 2: Stacking ratio 85% and above but less than 90% 1: Stacking ratio 90% and above

[0252] [Linewidth Sensitivity] The pixel width control at low exposure levels was evaluated using linewidth sensitivity. The obtained photosensitive coloring composition was spin-coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) using a spin-coating method to a dried film thickness of 2.5 μm, and dried using a vacuum dryer. Subsequently, exposure was performed using a high-pressure mercury lamp at an illuminance of 30 mW / cm² and an exposure of 25 mJ / cm², using a photomask. The photomask opening width was 50 μm, and the distance between the substrate and the photomask was 150 μm. Afterward, the mixture was developed by jet spray with a sodium carbonate aqueous solution at 23°C for 40 seconds, rinsed with deionized water, air-dried, and then heated in a clean oven at 230°C for 30 minutes. The pixel width of the obtained photolithography pattern was measured using an optical microscope (Olympus Optical BX-51, 500x magnification) and image processing software (ImagePro). A value of 3 or higher was considered practical. 5: (pixel width - photomask aperture width) ≥ 10 μm; 4: (pixel width - photomask aperture width) ≥ 8 μm and < 10 μm; 3: (pixel width - photomask aperture width) ≥ 6 μm and < 8 μm; 2: (pixel width - photomask aperture width) ≥ 2 μm and < 6 μm; 1: (pixel width - photomask aperture width) < 2 μm.

[0253] [Wrinkles] For the substrate used for evaluating the pattern formation, the pattern surface was observed using an optical microscope (Olympus Optical Corporation "BX-51", magnification: 200x). A score of 3 or higher is considered practical. 5: No wrinkles are observed on the pattern surface at all. 4: Very few wrinkles are observed on the pattern surface. 3: A small number of wrinkles are observed on the pattern surface. 2: Wrinkles are observed on the pattern surface. 1: Numerous wrinkles are observed on the pattern surface.

[0254] [Table 4] Table 4 Example 1 Example 2 Example 3 Example 4 Example 5 Example 6 Example 7 Example 8 Example 9 Example 10 Example 11 Heat resistance 5 5 5 5 5 4 5 5 5 5 5 Stacking height ratio 5 5 5 3 5 5 5 5 5 5 5 Line width sensitivity 5 5 5 5 5 5 5 5 4 5 4 folds 5 5 5 4 5 4 4 5 5 5 5 Example 12 Example 13 Example 14 Example 15 Example 16 Example 17 Example 18 Example 19 Example 20 Example 21 Example 22 Heat resistance 5 5 5 5 5 5 5 5 5 4 5 Stacking height ratio 5 5 5 5 5 5 5 5 4 5 5 Line width sensitivity 5 5 5 5 5 5 5 5 5 5 5 folds 5 5 5 5 5 5 5 5 5 5 5 Example 23 Example 24 Example 25 Example 26 Example 27 Example 28 Example 29 Example 30 Example 31 Comparative Example 1 Comparative Example 2 Heat resistance 5 5 5 5 5 5 5 3 5 5 2 Stacking height ratio 5 5 5 5 5 5 3 5 4 4 3 Line width sensitivity 5 5 5 5 5 5 5 3 3 2 5 folds 5 5 5 5 5 5 4 3 5 2 2 film thickness [Simplified Explanation of the Diagram]

[0016] Figure 1 shows a schematic cross-sectional view of the image display device. Figure 2 shows a schematic cross-sectional view of the evaluation of pixel and stacked light spacer height.

Claims

1. A photosensitive coloring composition comprising: a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the polymerizable compound (C) comprises a polyfunctional aminocarbamate (meth)acrylate (C1), and the photopolymerization initiator (D) comprises an oxime ester-based photopolymerization initiator (D2b) containing two oxime ester groups in one molecule, as represented by the following general formula (1), general formula (1) (wherein, In general formula (1), X1 and X2 independently represent carbonyl bonds (-CO-) or single bonds; X3 represents a single bond or a sulfur atom; R1 represents an alkyl group with 1 to 20 carbon atoms; R2 and R3 each independently represent a hydrogen atom or an alkyl group with 1 to 20 carbon atoms, and at least one of R2 and R3 is a straight-chain alkyl group with 1 to 20 carbon atoms; R4 and R5 each independently represent an alkyl group with 1 to 20 carbon atoms.

2. The photosensitive coloring composition as claimed in claim 1, wherein the polymeric compound (C) further comprises a polymeric compound (C2) having a viscosity of less than 800 mPa·S at 25°C (wherein, Except for urethane (meth)acrylates (C1).

3. The photosensitive coloring composition as claimed in claim 2, wherein the content of the polymeric compound (C2) with a viscosity of less than 800 mPa·S at 25°C is 5% to 50% by mass in 100% by mass of the polymeric compound (C).

4. The photosensitive coloring composition as claimed in any one of claims 1 to 3, wherein the colorant (A) comprises a phthalocyanine pigment with Al as the central metal.

5. The photosensitive coloring composition as claimed in any one of claims 1 to 3, wherein the polyfunctional aminocarbamate (meth)acrylate (C1) has 4 to 10 polymerizable unsaturated groups.

6. A color filter comprising: a substrate, and a filter segment formed of a photosensitive coloring composition as described in any one of claims 1 to 5.

7. An image display device having a color filter as described in claim 6.

8. A solid-state photographic element having a color filter as described in claim 6.

Images