Photosensitive colored composition, and color filter, solid-state image sensor, liquid crystal display device.

Abstract

The present invention aims to provide a photosensitive coloring composition that can achieve both maintenance of optical properties and improvement of pixel adhesion and shape under conditions of high colorant concentration, a color filter having a filter segment formed by the photosensitive coloring composition, a solid-state image sensor equipped with the color filter, and a liquid crystal display device. [Solution] The above problem is solved by a photosensitive colored composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the content of the colorant (A) is 45 parts by mass or more and 85 parts by mass or less per 100 parts by mass of the total nonvolatile content of the photosensitive colored composition contained in the photosensitive colored composition, and the polymerizable compound (C) comprises a polymerizable compound (C1) having one or more secondary hydroxyl groups and three or more polymerizable unsaturated groups.

Description

Technical Field

[0001] The present invention relates to a photosensitive coloring composition used in the production of a color filter used in a color liquid crystal display device such as a solid-state imaging device, and a color filter using the same.

Background Art

[0002] A color filter constituting a color liquid crystal display device (LCD), a solid-state imaging device, etc. is manufactured by applying a coating liquid (coloring composition) onto a transparent substrate and drying it to form a coating film having a thickness of about 0.3 to 3 μm.

[0003] Generally, a color filter used in a solid-state imaging device has a smaller pixel size and is a thinner film than an LCD. Also, the solid-state imaging device itself has been miniaturized. While the color filter is being made thinner, the chromaticity of the pixels needs to be maintained, so the concentration of the colorant in the coating film cannot be decreased. Therefore, while increasing the content of the colorant in the photosensitive coloring composition, other components (resin, polymerizable compound, photoinitiator, etc.) need to be relatively reduced in amount. As a result, problems have occurred such as the problem that no pixel pattern remains after the development process (poor adhesion), the problem that the rectangularity of the pixels deteriorates even if the pixel pattern remains (poor shape), and the problem that the formed pixel pattern deteriorates in a later process (poor resistance). Regarding the above problems, Patent Document 1 discloses a photosensitive coloring composition containing a binder resin having a defined acid value. Also, Patent Document 2 discloses a photosensitive coloring composition that can form a pattern with good solvent resistance and suppress development residues by containing a polymerizable compound having a specific structure containing two secondary hydroxyl groups, even when the content of the colorant is increased. Also, Patent Document 3 discloses a photosensitive coloring composition containing a polymerizable compound having a specific (meth)acryloyl group, one or more and twelve or less hydroxyl groups derived from a glycidyl group, and a branched structure, which has few residues in the unexposed portion after development and good pattern formability.

Prior Art Documents

Patent Documents

[0004] [Patent Document 1] Japanese Patent Publication No. 2019-168688 [Patent Document 2] Japanese Patent Publication No. 2024-150911 [Patent Document 3] Japanese Patent Publication No. 2012-14053 [Overview of the Initiative] [Problems that the invention aims to solve]

[0005] However, conventional photosensitive coloring compositions have problems in achieving both maintenance of optical properties and improvement of pixel adhesion and shape due to insufficient photocuring efficiency under conditions of high colorant concentration.

[0006] The present invention is characterized by containing a polymerizable compound (C1) that contains one or more secondary hydroxyl groups and three or more polymerizable unsaturated groups. This promotes even more efficient photocuring of the photosensitive colored composition, thereby solving the drawbacks of poor pixel adhesion and poor pixel pattern shape. Furthermore, the inclusion of the polymerizable compound (C1) forms a high molecular weight crosslinked structure, resulting in high solvent resistance. [Means for solving the problem]

[0007] In other words, the present invention relates to a photosensitive colored composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the content of the colorant (A) is 45 parts by mass or more and 85 parts by mass or less per 100 parts by mass of the total nonvolatile content of the photosensitive colored composition contained therein, and the polymerizable compound (C) comprises a polymerizable compound (C1) having one or more secondary hydroxyl groups and three or more polymerizable unsaturated groups.

[0008] The present invention relates to the photosensitive coloring composition characterized in that the polymerizable compound (C1) has two or more secondary hydroxyl groups and three polymerizable unsaturated groups.

[0009] The present invention relates to the photosensitive coloring composition characterized in that the polymerizable compound (C1) has two or more secondary hydroxyl groups and four or more polymerizable unsaturated groups.

[0010] The present invention relates to a photosensitive coloring composition in which the photopolymerization initiator (D) comprises a photopolymerization initiator (D1) having an oxime ester skeleton.

[0011] The present invention relates to a photosensitive colored composition characterized in that the resin (B) comprises a dispersion resin (B1), and the dispersion resin (B1) has polymerizable unsaturated groups.

[0012] The present invention relates to a color filter having a filter segment formed by the photosensitive colored composition.

[0013] The present invention relates to a solid-state image sensor equipped with the aforementioned color filter.

[0014] The present invention relates to a liquid crystal display device equipped with the aforementioned color filter. [Effects of the Invention]

[0015] The present invention provides a photosensitive coloring composition with good pixel rectangularity. Furthermore, by using the photosensitive coloring composition of the present invention, high-quality color filters, color liquid crystal display devices, solid-state image sensors, etc., with suppressed residue can be provided. [Brief explanation of the drawing]

[0016] [Figure 1] Figure 1 is a schematic cross-sectional view of a liquid crystal display device. [Modes for carrying out the invention]

[0017] The following describes each component of the photosensitive coloring composition of the present invention. In the present invention, when expressed as "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide", unless otherwise specified, they respectively represent "acryloyl and / or methacryloyl", "acrylic and / or methacrylic", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or methacrylamide". In addition, "C.I." mentioned in this specification means Color Index (C.I.).

[0018] <Photosensitive Coloring Composition> The photosensitive coloring composition in the present invention contains a colorant (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the content of the colorant (A) is 45 parts by mass or more and 85 parts by mass or less in 100 parts by mass of the total non-volatile content of the photosensitive coloring composition contained in the photosensitive coloring composition, and the polymerizable compound (C) contains a polymerizable compound (C1) containing one or more secondary hydroxyl groups and three or more ethylenically unsaturated bonds.

[0019] <Colorant (A)> Examples of the colorant (A) include dyes and pigments. Examples of the pigments include inorganic pigments and organic pigments, and organic pigments are preferred. The colorant (A) is contained in an amount of 45 parts by mass or more and 85 parts by mass or less in 100 parts by mass of the total non-volatile content of the photosensitive coloring composition. Thereby, a good chromaticity can be obtained while the pattern is a thin film. The above content is more preferably 54 parts by mass or more and 70 parts by mass or less.

[0020] Hereinafter, the colorant (A) will be exemplified. For example, red pigments include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 14, 17, 22, 23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 57:1, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90, 105, 112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170, 171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200, 202 Examples include, but are not limited to, azo pigments described in Japanese Patent Publication No. 2014-112527, azo pigments described in Japanese Patent Publication No. 2013-161026, or diketopyrrolopyrrole pigments described in Japanese Patent Publication No. 2011-523433. Among these, CI Pigment Red 177, CI Pigment Red 254, CI Pigment Red 269, and CI Pigment Red 272 are preferred in terms of high transmittance.

[0021] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, and 73, but the range is not limited to these. Among these, CI Pigment Orange 71 is preferred for reproducing the color gamut of the color filter. For example, yellow pigments include CI Pigment Yellow 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73 ,74,75,81,83,87,93,94,95,97,100,101,104,105,108,109,110,111,116,117,119,120,126,127,127:1,128,129,133,134,136,138,139,142,147,148,150 Examples include, but are not limited to, quinophthalone compounds described in Japanese Patent Publication No. 2012-226110, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, 231, 233, and quinophthalone compounds described in Japanese Patent Publication No. 2012-226110. Among these, CI Pigment Yellow 138, 139, 150, 185 and the quinophthalone compounds described in Japanese Patent Publication No. 2012-226110 are preferred for reproducing the color gamut of the color filter.

[0022] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63. Among these, CI Pigment Green 7, 36, 58, 59, 62, and 63 are preferred from the viewpoint of brightness and coloring power. In addition, zinc phthalocyanine pigments described in Japanese Patent Publication No. 2008-19383, Japanese Patent Publication No. 2007-320986, Japanese Patent Publication No. 2004-70342, etc., and aluminum phthalocyanine pigments described in Japanese Patent Publication No. 2004-333817, Japanese Patent Publication No. 2012-247588, etc. can be used. For blue pigments, for example, CIPigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 22, 60, 64, 80, etc. can be used. For purple pigments, for example, CIPigment Violet 1, 19, 23, 27, 29, 30, 32, 37, 40, 42, 50, etc. can be used. For black pigments, for example, carbon black, aniline black, anthraquinone-based black pigments, and perylene-based black pigments can be used, specifically CI Pigment Black 1, 6, 7, 12, 20, 31, etc. Other examples include rhodamine-based metallic lake pigments such as CI Pigment Red 81, 81:1, 81:2, 81:3, 81:4, and 81:5.

[0023] In addition, examples of inorganic pigments include metal oxide powders such as silicon dioxide, zirconia oxide, barium sulfate, zinc oxide, lead sulfate, lead yellow, zinc yellow, red iron(III) oxide, cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, amber, titanium black, synthetic iron black, titanium dioxide, and iron tetroxide, as well as metal sulfide powders and metal powders.

[0024] Furthermore, any of the following dyes can be used: acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Derivatives of these dyes, or even lake pigments (dyes prepared by lake formation), are also acceptable.

[0025] Acid dyes preferably have acidic groups such as sulfonic acid or carboxylic acid. Direct dyes preferably form salt compounds with an inorganic salt of the acid dye, or with an acid dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, tertiary amine compound, secondary amine compound, or primary amine compound. Salt compounds that are salts of a resin component having these functional groups and an acid dye are also preferred. Furthermore, by sulfonamidating the salt compound to a sulfonic acid amide compound, it is easy to obtain a photosensitive colored composition with excellent resistance (lightfastness, solvent resistance). Furthermore, salt-forming compounds of acid dyes and compounds containing an onium base are also preferred due to their excellent resistance (light resistance and solvent resistance). The compound containing the onium base is preferably a resin having a cationic group.

[0026] Basic dyes can be used as is, but salt compounds formed by chlorinating with organic acids, perchloric acid, or their metal salts are preferred. Salt compounds of basic dyes are preferred because they have excellent resistance (lightfastness, solvent resistance) and affinity with pigments. Furthermore, in salt compounds of basic dyes, preferred anionic components that act as counterions are salt compounds formed by chlorinating with organic sulfonic acids, organic sulfuric acids, fluorine-containing phosphorus anionic compounds, fluorine-containing boron anionic compounds, cyano-containing nitrogen anionic compounds, anionic compounds having a conjugate base of an organic acid with a halogenated hydrocarbon group, and acid dyes. Note that the resistance of the salt compound is further improved if it contains polymerizable unsaturated groups in its molecule.

[0027] Furthermore, if the pigment skeleton has polymerizable unsaturated groups, it can be used to produce a dye with excellent resistance, which is preferable.

[0028] Examples of dye chemical structures include azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (oxazine dyes, thiazine dyes, etc.), and azine. Examples of pigment structures derived from dyes selected from the following: polymethine dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

[0029] Among these pigment structures, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, pigment structures derived from pigments selected from azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and pigment structures derived from pigments selected from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyromethene dyes, and phthalocyanine dyes are more preferred. Specific pigment compounds that can form pigment structures are described in "New Edition Dye Handbook" (edited by the Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyers and colourists), and "Pigment Handbook" (edited by Okawara et al.; Kodansha, 1986), among others.

[0030] Furthermore, the dye derivative (b) described later, which may be added as needed in the present invention, is classified as a colorant.

[0031] Coloring agent (A) can be used alone or in combination of two or more types.

[0032] <Pigment miniaturization> The method for micronizing the pigment used in the photosensitive colored composition of the present invention is not particularly limited. For example, wet grinding, dry grinding, or dissolution extraction methods can all be used. As exemplified in the present invention, micronization can be performed by salt milling using a kneader method, which is a type of wet grinding. The average primary particle size of the pigment, as determined by TEM (transmission electron microscope), is preferably in the range of 10 to 80 nm. If it is smaller than 10 nm, dispersion in the organic solvent becomes difficult, and if it is larger than 80 nm, a sufficient contrast ratio may not be obtained. For these reasons, a more preferable average primary particle size is in the range of 15 to 70 nm.

[0033] Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and water-soluble organic solvent is mechanically kneaded while heated using batch or continuous kneading machines such as kneaders, two-roll mills, three-roll mills, ball mills, attritors, sand mills, and planetary mixers, and then washed with water to remove the water-soluble inorganic salt and water-soluble organic solvent. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for salt milling the pigment, it is possible to obtain pigments with a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

[0034] As water-soluble inorganic salts, sodium chloride, barium chloride, potassium chloride, sodium sulfate, etc., can be used, but from a cost standpoint, sodium chloride (table salt) is preferred. From the perspective of both processing efficiency and production efficiency, it is preferable to use 50 to 2000 parts by mass of water-soluble inorganic salt per 100 parts by mass of pigment, and most preferably 300 to 1000 parts by mass.

[0035] The water-soluble organic solvent serves to wet the pigment and the water-soluble inorganic salt. It is not particularly limited as long as it dissolves (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is prone to evaporation, a high-boiling-point solvent with a boiling point of 120°C or higher is preferred from a safety standpoint. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The water-soluble organic solvent is preferably used in an amount of 5 to 1000 parts by mass, and most preferably 50 to 500 parts by mass, per 100 parts by mass of pigment.

[0036] When the pigment is subjected to salt milling, a resin may be added as needed. The type of resin used is not particularly limited, and natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, etc., can be used. The resin used is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in the above organic solvent. The amount of resin used is preferably in the range of 5 to 200 parts by mass per 100 parts by mass of pigment.

[0037] <Metal Removal> If specific metal elements are present in large quantities as impurities other than the pigment components in the colored composition, it can impair the dispersion stability over time, and may also reduce heat resistance or sensitivity. Furthermore, color filters made using such compositions may develop foreign matter, which can easily lead to a decrease in brightness. It is preferable that the total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) in the photosensitive colored composition is 500 ppm by mass or less.

[0038] The total amount of specific metal elements contained in the photosensitive colored composition is more preferably 300 ppm by mass or less, and particularly preferably 200 ppm by mass or less. Furthermore, while there is no particular lower limit to the total amount of specific metal elements, it is preferably 1 ppm by mass or more, and more preferably 5 ppm by mass or more. Within the above range, a photosensitive colored composition can be obtained that suppresses costs, has excellent storage stability, and can form a color filter with minimal generation of foreign matter and reduction in brightness.

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

[0040] Furthermore, it is preferable that the metals that make up the pigment, such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co, contain fewer impurities that do not function effectively, and these can be removed in the same way as specific metal elements by the following methods. In addition, it is preferable that the concentrations of Mn, Cs, Ti, Co, Si, Pd, etc., that have been introduced due to materials used in the manufacturing process of the various raw materials of the photosensitive colored composition (for example, catalysts) be low.

[0041] Methods for removing colorants (A) or metals introduced from equipment during the manufacturing process include washing with water as described in Japanese Patent Publication No. 2010-83997, Japanese Patent Publication No. 2018-36521, Japanese Patent Publication No. Hei 7-198928, Japanese Patent Publication No. Hei 8-333521, Japanese Patent Publication No. 2009-7432, etc., and methods for removing magnetic foreign matter using a magnet as described in Japanese Patent Publication No. 2011-48736, and one or more of these methods may be used as appropriate.

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

[0043] <Dye derivative (b)> The photosensitive colored composition of the present invention can use a dye derivative (b). The dye derivative (b) is a compound having an acidic group, a basic group, a neutral group, etc., in an organic dye residue. Examples include compounds having acidic substituents such as a sulfo group, a carboxyl group, or a phosphate group, and their amine salts; compounds having basic substituents such as a sulfonamide group or a tertiary amino group at the terminal; and compounds having neutral substituents such as a phenyl group or a phthalimidoalkyl group. Since the dispersion resin (B1) used in combination has an acidic group, a dye derivative having a basic group is preferred. Examples of organic pigments in organic pigment residues include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiaidine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, surene pigments, metal complex pigments, azo pigments such as azo, disazo, and polyazo, and so on. These dye derivatives (b) can be used individually or in combination of two or more types.

[0044] The amount of dye derivative (b) used is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, and even more preferably 5 to 20 parts by mass, per 100 parts by mass of colorant (A).

[0045] By adding a pigment derivative (b) to the pigment and performing a micronization treatment such as acid pasting, acid slurry, dry milling, salt milling, or solvent salt milling, the pigment derivative is adsorbed onto the pigment surface, and the primary particles of the pigment can be made finer compared to when no pigment derivative is added.

[0046] <Resin (B)> Resin (B) preferably contains a dispersion resin (B1). Furthermore, resin (B) preferably contains an alkali-soluble resin (B2).

[0047] <Dispersion resin (B1)> The dispersion resin (B1) has adsorption sites that adsorb to the colorant and steric repulsion sites that disperse the colorant. The dispersion resin (B1) is not particularly limited, and known resins can be used. Examples of dispersion resins (B1) include urethane resins, 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 polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, amides and salts thereof formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyester systems, modified polyacrylate systems, ethylene oxide / propylene oxide adduct compounds, and phosphate ester systems. Furthermore, examples of polymeric dispersants having basic functional groups include nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers and urethane polymeric dispersants having functional groups in their side chains that include tertiary amino groups, quaternary ammonium bases, nitrogen-containing heterocycles, etc.

[0048] Commercially available dispersion resins (B1) are Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 21 SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21 00, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500, etc., as well as BASF Japan's EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080 Examples include 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., as well as Ajispa-PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine Techno Co., Ltd.

[0049] The dispersion resin (B1) preferably has polymerizable unsaturated groups. Because the dispersion resin (B1) has polymerizable unsaturated groups, it has photosensitivity in addition to its normal dispersion performance. Therefore, in compositions with high pigment concentrations, the crosslinking density of the formed film is further improved by light irradiation, and the pattern shape of the pixels is improved.

[0050] The content of the dispersion resin (B1) is preferably 1 to 20% by mass, and more preferably 2 to 17% by mass, based on 100% by mass of the nonvolatile content of the photosensitive colored composition.

[0051] <Alkali-soluble resin (B2)> The alkali-soluble resin (B2) is, for example, a resin having acidic groups such as carboxyl groups and sulfone groups. This allows photolithography properties to be imparted to the film formed from the photosensitive colored composition.

[0052] Examples of alkali-soluble resins (B2) include acrylic resins, α-olefin / (anhydride) maleic acid copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (anhydride) maleic acid copolymers. Among these, acrylic resins and styrene / styrene sulfonic acid copolymers are preferred.

[0053] Alkali-soluble resins (B2) can be classified into alkali-soluble resins without polymerizable unsaturated groups (B2-1) and alkali-soluble resins with polymerizable unsaturated groups (B2-2).

[0054] The weight-average molecular weight (Mw) of the alkali-soluble resin (B2) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and even more preferably 4,000 to 20,000, in order to impart alkali-developable solubility. Furthermore, the Mw / Mn value is preferably 10 or less. Having an appropriate weight-average molecular weight (Mw) makes it easier to achieve both improved adhesion and suppression of development residue. The acid value of the alkali-soluble resin (B2) is preferably 50-200 mgKOH / g, more preferably 70-180 mgKOH / g, and even more preferably 90-170 mgKOH / g. Having an appropriate acid value makes it easier to achieve both improved adhesion and suppression of developing residue.

[0055] <Alkali-soluble resin (B2-1) without polymerizable unsaturated groups> The alkali-soluble resin (B2-1) that does not have polymerizable unsaturated groups can be appropriately selected from resins such as the acrylic resins already exemplified, and from resins obtained by removing polymerizable unsaturated groups from the alkali-soluble resin (B2-2) described below.

[0056] <Alkali-soluble resin having polymerizable unsaturated groups (B2-2)> The alkali-soluble resin (B2-2) having polymerizable unsaturated groups includes, for example, resins to which polymerizable unsaturated groups have been added, such as the acrylic resins already exemplified. In this specification, resins synthesized by, for example, the methods described in (i) and (ii) below are preferred. This results in a higher crosslinking density upon light irradiation of the film formed from the photosensitive colored composition.

[0057] [Method (i)] Method (i) is, for example, to first synthesize polymers of epoxy group-containing monomers and other monomers. Then, a carboxyl group-containing monomer is added to the epoxy group of the polymer, and a polybasic acid anhydride is reacted with the resulting hydroxyl group to obtain an alkali-soluble resin (B2).

[0058] Examples of epoxy group-containing monomers include glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

[0059] Monocarboxyl group-containing monomers include, for example, (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and monocarboxylic acids such as α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted derivatives of (meth)acrylic acid.

[0060] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0061] Monomers and polybasic acid anhydrides can be used individually or in combination of two or more types.

[0062] Another method similar to method (i) involves, for example, synthesizing a carboxyl group-containing monomer and other monomers to produce a polymer. Then, an epoxy group-containing monomer is added to some of the carboxyl groups of the polymer to obtain an alkali-soluble resin (B2).

[0063] [Method (ii)] Method (ii) involves, for example, synthesizing a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers to produce a polymer. Then, the hydroxyl group of the polymer is reacted with the isocyanate group of the isocyanate group-containing monomer.

[0064] The hydroxyl group-containing monomers that have already been exemplified can be used. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred because they are less likely to produce foreign matter in the coating. In addition, glycerol mono(meth)acrylate is preferred in terms of light sensitivity.

[0065] Examples of monomers having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0066] Other monomers that can be used in the synthesis of alkali-soluble resin (B2) include, for example, (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate. Alternatively, examples include (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or styrenes such as acryloylmorpholine, or styrenes such as α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and vinyl fatty acid compounds such as vinyl acetate or vinyl propionate.

[0067] Cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidediphenylmethane, bis(3-ethyl-5-methyl-4-maleimidephenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N Examples include N-substituted maleimides such as -(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzoimidazolyl)phenyl]maleimide, and 9-maleimide acridine, as well as monomers represented by the following general formula (1). Monomers represented by general formula (1) include, for example, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol. EO stands for ethylene oxide, and PO stands for propylene oxide.

[0068] General formula (1) [ka]

[0069] (In general formula (1), R6 is a hydrogen atom or a methyl group, R7 is an alkylene group having 2 or 3 carbon atoms, R8 is an alkyl group having 1 to 20 carbon atoms which may have a benzene ring, and n is an integer from 1 to 15.)

[0070] Furthermore, examples of hydroxyl group-containing monomers include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. In addition, examples of polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide, etc., to the above hydroxyalkyl (meth)acrylates, and (poly)ester mono(meth)acrylates obtained by adding (poly)γ-valerolactone, (poly)ε-caprolactone, and / or (poly)12-hydroxystearic acid, etc.

[0071] The alkali-soluble resin (B2) content is preferably 0.1 to 20% by mass, and more preferably 0.2 to 10% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0072] Resin (B) can be used alone or in combination of two or more types. The total content of resin (B) is preferably 1 to 20% by mass, and more preferably 2 to 17% by mass, based on 100% by mass of the nonvolatile content of the photosensitive colored composition.

[0073] <Polymerizable compound (C)> Polymerizable compound (C) includes monomers and oligomers having polymerizable unsaturated groups. Examples of polymerizable compound (C) include polymerizable compound (C1) containing one or more secondary hydroxyl groups and three or more polymerizable unsaturated groups, polymerizable compounds having acid groups, polymerizable compounds having urethane bonds, and other polymerizable compounds. The photosensitive colored composition of the present invention is characterized by containing polymerizable compound (C1) containing one or more secondary hydroxyl groups and three or more polymerizable unsaturated groups.

[0074] (A polymerizable compound (C1) containing one or more secondary hydroxyl groups and three or more polymerizable unsaturated groups) By including a polymerizable compound (C1) containing one or more secondary hydroxyl groups and three or more polymerizable unsaturated groups, the overall polarity of the coating film is increased, reducing its affinity for nonpolar oxygen and making oxygen inhibition during photocuring less likely. As a result, a higher molecular weight crosslinked structure can be formed during photocuring, making it less soluble in alkaline developers, and improving the adhesion and rectangularity of the formed pixels. Furthermore, high solvent resistance can be obtained by forming a high molecular weight crosslinked structure. A polymerizable compound (C1) containing one or more secondary hydroxyl groups and three or more polymerizable unsaturated groups may also have acid groups or urethane bonds.

[0075] Furthermore, it is preferable that the polymerizable compound (C1) has two or more secondary hydroxyl groups and three polymerizable unsaturated groups.

[0076] Furthermore, it is more preferable that the polymerizable compound (C1) has two or more secondary hydroxyl groups and four or more polymerizable unsaturated groups.

[0077] Polymerizable compounds (C1) containing one or more secondary hydroxyl groups and three or more polymerizable unsaturated groups can be synthesized by reacting trifunctional or higher epoxy compounds with compounds having carboxylic acid groups and polymerizable groups, such as acrylic acid and methacrylic acid. Other polymerizable compounds having carboxylic acid groups include Examples of unsaturated monocarboxylic acids include β-carboxyethyl (meth)acrylate, 2-(meth)acryloyloxyethyl succinic acid, ω-carboxypolycaprolactone mono(meth)acrylate, 2-(meth)acryloyloxyethyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hydrogen phthalate, 2-(meth)acryloyloxypropyl hexahydrohydrogen phthalate, and 2-(meth)acryloyloxypropyl tetrahydrohydrogen phthalate. Examples of epoxy compounds with three or more functions include epoxy compounds containing glycidylamines such as 4,4′-methylenebis(N,N-diglycidylaniline), triglycidyl-p-aminophenol, N,N,N′,N′-tetraglycidyl-m-xylenediamine, and 1,3-bis(diglycidylaminomethyl)cyclohexane, phloroglucinol triglycidyl ether, trihydroxybiphenyl triglycidyl ether, tris(4-hydroxyphenyl)methane triglycidyl ether, tetraphenylolethane glycidyl ether, triglycidyl cyanurate, tris(2,3-epoxypropyl) isocyanurate, and sorbitol polyglycidyl ether. Examples include, but are not limited to, polyfunctional aliphatic epoxy compounds selected from the group consisting of methyl ether, glycerol polyglycidyl ether, diglycerol polyglycidyl ether, polyglycerol polyglycidyl ether, pentaerythritol tetraglycidyl ether, and trimethylolpropane triglycidyl ether, triglycidyl isocyanurates, and other glycidylamine-based epoxy resins, as well as aliphatic epoxy resins of epoxidized polybutadiene and epoxidized oils and fats, phenol novolac epoxy resins, cresol novolac epoxy resins, EHPE-3150 (manufactured by Daicel Chemical Industries, Ltd., alicyclic epoxy resin), and polyfunctional alicyclic epoxy resins.

[0078] Examples of commercially available polymerizable compounds (C1) containing one or more secondary hydroxyl groups and three or more polymerizable unsaturated groups include EBECRYL860 (manufactured by Daicel Ornex Co., Ltd.) and EA5312 (manufactured by Shin Nakamura Chemical Co., Ltd.).

[0079] The content of polymerizable compound (C1), which contains one or more secondary hydroxyl groups and three or more polymerizable unsaturated groups, is preferably 1 to 30% by mass, and more preferably 2 to 25% by mass, based on 100% by mass of the nonvolatile content of the photosensitive colored composition.

[0080] (Polymerizable compounds containing acidic groups) The polymerizable compound (C) in the present invention may contain polymerizable compounds having acidic groups. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups. However, in the present invention, compounds containing one or more secondary hydroxyl groups and three or more polymerizable unsaturated groups are not included in polymerizable compounds having acidic groups.

[0081] Examples of polymerizable compounds having acidic groups include poly(meth)acrylates containing free hydroxyl groups of polyhydric alcohols and (meth)acrylic acid, esterified with dicarboxylic acids; esterified polycarboxylic acids and monohydroxyalkyl (meth)acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, and monoesterified poly(meth)acrylates containing free carboxyl groups of dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; and propane-1,2,3-tricarboxylic acid (tricarvalic acid). Examples include oligoesters containing free carboxyl groups formed by the interaction of tricarboxylic acids such as butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid with monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate, but the effects of the present invention are not limited to these.

[0082] Suitable commercially available polymerizable compounds having the aforementioned acid group include Viscoat #2500P from Osaka Organic Co., Ltd., and Aronics M-5300, M-5400, M-5700, M-510, M-520, etc. from Toagosei Co., Ltd.

[0083] (Polymerizable compound containing urethane bonds) The polymerizable compound (C) in the present invention may include polymerizable compounds containing at least one ethylenically unsaturated bond and at least one urethane bond. Examples include polyfunctional urethane acrylates obtained by reacting a polyfunctional isocyanate with a hydroxyl group-containing (meth)acrylate, and polyfunctional urethane acrylates obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting that with a hydroxyl group-containing (meth)acrylate. However, in the present invention, compounds containing one or more secondary hydroxyl groups and three or more polymerizable unsaturated groups are not included in polymerizable compounds having urethane bonds.

[0084] Examples of (meth)acrylates containing hydroxyl groups include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, and hydroxyl group-containing polyol polyacrylates.

[0085] Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanates.

[0086] Suitable commercially available polymerizable compounds having the aforementioned urethane bond include AH-600, AT-600, UA-306H, UA-306T, UA-306I, UA-510H, UF-8001G, and DAUA-167 from Kyoeisha Chemical Co., Ltd., UA-160TM from Shin Nakamura Chemical Industry Co., Ltd., and UV-4108F and UV-4117F from Osaka Organic Chemical Industry Co., Ltd.

[0087] (Other polymerizable compounds) Other polymerizable compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanurate EO-modified di(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol Examples include, but are not limited to, acrylic acid esters and methacrylic acid esters such as tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, methylolated melamine (meth)acrylate, epoxy(meth)acrylate, urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0088] Other commercially available polymerizable compounds include KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, DPCA-120 from Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, M-310, M-32 from Toagosei Co., Ltd. 1. Suitable products include M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400, #405 from Osaka Organic Chemicals Co., Ltd., and NK Ester A-9300 from Shin Nakamura Chemical Co., Ltd.

[0089] The polymerizable compound (C) can be used alone or, if necessary, by mixing two or more types in any ratio.

[0090] The total content of polymerizable compound (C) is preferably 1 to 30% by mass, and more preferably 2 to 25% by mass, based on 100% by mass of the nonvolatile content of the photosensitive colored composition. Furthermore, the content of polymerizable compound (C1) is preferably 50 to 100% by mass, and more preferably 70 to 100% by mass, based on 100% by mass of polymerizable compound (C).

[0091] <Photopolymerization initiator (D)> The photosensitive coloring composition of the present invention contains a photopolymerization initiator (D). The photopolymerization initiator (D) preferably contains a photopolymerization initiator (D1) having an oxime ester skeleton (hereinafter referred to as oxime ester-based photopolymerization initiator (D1)).

[0092] (Oxime ester-based photopolymerization initiator (D1)) The oxime ester-based photopolymerization initiator (D1) undergoes cleavage of the NO bond in the oxime upon absorption of ultraviolet light, generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, allowing for pattern formation with less exposure compared to other photopolymerization initiators. This improves photocurability and enhances the pattern shape of the pixels.

[0093] Oxime ester photopolymerization initiators (D1) can be classified by their molecular skeleton into oxime ester photopolymerization initiators having a carbazole skeleton, a fluorene skeleton, or a diphenyl skeleton, as well as oxime ester photopolymerization initiators having two oxime ester groups. Furthermore, preferred specific molecular structures include hydroxyl groups, nitro groups, carbonyl groups, fluorinated carbon groups, and benzofurans.

[0094] (Oxime ester-based photopolymerization initiators having a diphenyl skeleton) Examples of oxime ester-based photopolymerization initiators having a diphenyl skeleton and one oxime ester group are listed below. [ka]

[0095] (Oxime ester photopolymerization initiator with a carbazole skeleton) Examples of oxime ester-based photopolymerization initiators having a carbazole skeleton and one oxime ester group are listed below. [ka] JPEG2026098942000005.jpg104149

[0096] (Oxime ester photopolymerization initiator having a fluorene skeleton) Examples of oxime ester-based photopolymerization initiators having a fluorene skeleton and one oxime ester group are listed below. [ka]

[0097] (Oxime ester-based photopolymerization initiator having two oxime ester groups) Examples of oxime ester-based photopolymerization initiators include those having two oxime ester groups on either side of a carbazole skeleton or a phenothiazine skeleton, as shown below. [ka]

[0098] Among these, oxime ester photopolymerization initiators having a carbazole structure, oxime ester photopolymerization initiators having a diphenyl skeleton, and oxime ester photopolymerization initiators having two oxime ester groups (including those having a carbazole skeleton) are preferred, with oxime ester photopolymerization initiators having a carbazole structure being the most preferred. Furthermore, for oxime ester photopolymerization initiators having a diphenyl skeleton, if the molecular weight of the radical compound generated during exposure is high, the mobility within the coating film decreases and the radical reactivity with polymerizable compounds decreases. Therefore, it is preferable that the terminal end of the ester group in the oxime ester group does not become a phenyl ester.

[0099] Other oxime ester-based photopolymerization initiators include, for example, 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropane-1-one, 2-benzoyloxyimino-1-phenylpropane-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropane-1-one.

[0100] As oxime ester-based photopolymerization initiators (D1), the compounds described in Japanese Patent Publication No. 2001-233842, Japanese Patent Publication No. 2000-80068, Japanese Patent Publication No. 2006-342166, Japanese Patent Publication No. 1653-1660, Japanese Patent Publication No. 1653-1660, Japanese Patent Publication No. 1656-162, Journal of Photopolymer Science and Compounds described in Technology (1995, pp. 202-232), compounds described in JP 2000-66385, compounds described in JP 2000-80068, compounds described in JP 2004-534797, compounds described in JP 2006-342166, compounds described in JP 2017-19766, compounds described in Japanese Patent No. 6065596, International Publication Examples include compounds described in WO2015 / 152153, compounds described in International Publication WO2017 / 051680, compounds described in JP 2007-210991, compounds described in JP 2009-179619, compounds described in JP 2010-037223, compounds described in JP 2010-215575, and compounds described in JP 2011-020998.

[0101] In addition to the oxime ester-based photopolymerization initiator (D1), other photopolymerization initiators can be used in combination with the photopolymerization initiator (D). Other photopolymerization initiators include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4- Acetophenone compounds such as methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyldimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylic benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t- Benzophenone compounds such as butylperoxycarbonyl)benzophenone; thioxanthone compounds such as thioxanthone, 2-chlorthioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis( Triazine compounds such as trichloromethyl-(4'-methoxystyryl)-6-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Examples include phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds.

[0102] The content of the photopolymerization initiator (D) is preferably 0.1 to 20 parts by mass, and more preferably 0.2 to 10 parts by mass, per 100 parts by mass of the nonvolatile content of the photosensitive composition. Adding an appropriate amount improves photocurability and further suppresses developing residue.

[0103] <Organic solvent (S)> The organic solvent (S) is not particularly limited, and known compounds can be used. For example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methyl Butyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, toluene, o-chlorotoluene, benzene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butyl Benzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone,Examples include dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, etc.

[0104] <Thermosetting compound (E)> In the present invention, the resin (B) may include a thermosetting compound (E). When producing a color filter using the coloring composition for color filters of the present invention, including a thermosetting compound allows the composition to react during the firing of the filter segment, increasing the crosslinking density of the coating film. This improves the heat resistance of the filter segment, suppresses pigment aggregation during the firing of the filter segment, and improves the contrast ratio.

[0105] The thermosetting compound (E) may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. Examples of thermosetting compounds (E) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds, but the present invention is not limited thereto. In the coloring compositions for color filters of the present invention, epoxy compounds and oxetane compounds are preferably used.

[0106] (Epoxy compound) The epoxy compound can be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. Examples of such epoxy compounds include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropyl alcohol). Examples include polymers of penylbiphenyl (such as butadiene, isoprene), polycondensates of phenols and ketones (such as acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, and benzophenone), polycondensates of phenols and aromatic dimethanols (such as benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, and α,α,α',α'-biphenyldimethanol), polycondensates of phenols and aromatic dichloromethyls (such as α,α'-dichloroxylene and bischloromethylbiphenyl), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins, but are not limited to these as long as they are commonly used epoxy compounds. These may be used individually or in combination of two or more.

[0107] Commercially available products include, for example, Epicote 807, Epicote 815, Epicote 825, Epicote 827, Epicote 828, Epicote 190P, Epicote 191P (all product names; manufactured by Yuka Shell Epoxy Co., Ltd.), Epicote 1004, Epicote 1256 (all product names; manufactured by Japan Epoxy Resin Co., Ltd.), TECHMORE VG3101L (product name; manufactured by Mitsui Chemicals, Inc.), EPPN-501H, 502H (product name; manufactured by Nippon Kayaku Co., Ltd.), JER 1032H60 (product name; manufactured by Japan Epoxy Resin Co., Ltd.), JER 157S65, 157S70 (product name; manufactured by Japan Epoxy Resin Co., Ltd.), EPPN-201 (product name; manufactured by Nippon Kayaku Co., Ltd.), JER152, JER154 (product names; manufactured by Japan Epoxy Resin Co., Ltd.), EOCN-102S, EOCN-103S, EOCN-104S, EOCN-1020 (product names; manufactured by Nippon Kayaku Co., Ltd.), Ceroxide 2021, EHPE- Examples include 3150 (product name; manufactured by Daicel Chemical Industries), Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 (product names; manufactured by Nagase ChemteX), TEPIC-L, TEPIC-H, TEPIC-S (manufactured by Nissan Chemical Industries), etc. These are some examples, but are not limited to them.

[0108] The amount of epoxy compound blended is preferably 0.5 to 20 parts by mass, and more preferably 1.0 to 10 parts by mass, per 100 parts by mass of colorant. If the amount is less than 0.5 parts by mass, the effect of improving heat resistance is small, and if it is more than 20 parts by mass, problems may occur when forming filter segments by photolithography.

[0109] (Oxetane compounds) The photosensitive colored composition of the present invention preferably contains an oxetane compound. The oxetane compound can be any known compound having an oxetane group, without particular limitation. Examples of oxetane compounds include those with a monofunctional oxetane group, those with a bifunctional oxetane group, and those with two or more functional oxetane groups.

[0110] Examples of monofunctional oxetane groups include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyl oxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane. Specific examples include OXE-10 and OXE-30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and OXT-212 manufactured by Toagosei Co., Ltd.

[0111] Examples of difunctional oxetane groups include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethyleneglycosyl bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl Examples include bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, EO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, PO modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl) ether, and EO modified bisphenol F (3-ethyl-3-oxetanylmethyl) ether. Specific examples include OXBP and OXTP manufactured by Ube Industries, and OXT-121 and OXT-221 manufactured by Toagosei Co., Ltd.

[0112] As for substances with two or more oxetane groups, Pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa Examples of polymers include (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing oxetane groups (for example, the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30. Such polymers can be obtained using known polymerization methods.

[0113] The oxetane compound content in the photosensitive coloring composition of the present invention is typically 0.5 to 20 parts by mass, preferably 1 to 10 parts by mass, per 100 parts by mass of the coloring agent. A content of the oxetane compound within this range is preferable because it yields a coating film with excellent chemical resistance.

[0114] (Melamine compound) In this invention, the term "melamine compound" refers to a compound having a melamine ring structure. The melamine compound may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin. In this invention, preferred melamine compounds are of the methylol type or ether type, with 5.0 or more methylol groups and / or ether groups per melamine ring. If the number of methylol groups and / or ether groups per melamine ring is less than 5.0, there are fewer reaction sites, and the crosslinked structure during curing may not be sufficiently dense, resulting in a reduced effect on improving the heat resistance and chemical resistance of the coating film.

[0115] Examples of commercially available products include, but are not limited to, Nikarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, MX-410 (manufactured by Sanwa Chemical Co., Ltd.), and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 (manufactured by Japan Cytec Industries Co., Ltd.).

[0116] Among these, Nikarac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45 (manufactured by Sanwa Chemical Co., Ltd.), and Cymel 232, 235, 236, 238, 300, 301, 303, 350 (manufactured by Nippon Cytec Industries Co., Ltd.), which have 5.0 or more methylol groups and / or ether groups per melamine ring, are preferred because they can obtain a dense crosslinked structure.

[0117] (Hardening agent) Furthermore, the coloring composition for color filters of the present invention may optionally contain a curing agent (curing accelerator) to assist in the curing of the thermosetting compound. Effective curing agents include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds, but are not limited to these; any curing agent that can react with the thermosetting compound may be used. Examples of curing agents include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2) These can be used as curing accelerators, such as phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, phosphorus compounds (e.g., triphenylphosphine), and S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine isocyanuric acid adduct, etc.). These may be used individually or in combination of two or more. The content of the curing accelerator is preferably 0.01 to 15 parts by mass per 100 parts by mass of the thermosetting compound.

[0118] <Sensitizer (F)> Furthermore, the photosensitive coloring composition of the present invention may contain a sensitizer (F). Examples of sensitizers (F) include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as oxonol derivatives, acridine derivatives, azine derivatives, thiaidine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, and tetrapyradinoporphyrazine derivatives. Examples include phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaliloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrillium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospilopyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acylphosphine oxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc.

[0119] Among the above-mentioned sensitizers (F), thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives are particularly suitable for sensitization. More specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, etc. are used.

[0120] These sensitizers (F) can be used individually or mixed in any ratio of two or more as needed. Examples of commercially available products include "KAYACURE DETX-S" (2,4-diethylthioxanthone, manufactured by Nippon Kayaku Co., Ltd.) and "CHEMARK DEABP" (4,4'-bis(diethylamino)benzophenone, manufactured by Chemark Chemical Co., Ltd.).

[0121] More specifically, examples of sensitizers include, but are not limited to, those described in "Pigment Handbook" (1986, Kodansha) edited by Shin Okawara et al., "Chemistry of Functional Pigments" (1981, CMC) edited by Shin Okawara et al., and "Special Functional Materials" (1986, CMC). In addition, sensitizers that exhibit absorption in the ultraviolet to near-infrared region can also be included.

[0122] When using the sensitizer (F), the content is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the photoradical polymerization initiator contained in the colored composition, and more preferably 5 to 50 parts by mass from the viewpoint of photocurability and developability.

[0123] <Thiol-based chain transfer agent (G)> The photosensitive colored composition of the present invention preferably contains a thiol-based chain transfer agent. By using thiols together with a photopolymerization initiator, thiyl radicals are generated in the radical polymerization process after light irradiation that act as chain transfer agents and are less susceptible to polymerization inhibition by oxygen, resulting in a highly sensitive colored composition.

[0124] Furthermore, polyfunctional aliphatic thiols bonded to aliphatic groups such as methylene or ethylene groups, which have two or more SH groups, are preferred. More preferably, polyfunctional aliphatic thiols with four or more SH groups are preferred. Increasing the number of functional groups improves the polymerization initiation function, allowing curing from the surface of the pattern to near the substrate.

[0125] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, and pen Examples include tetraerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferably, examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0126] These thiol-based chain transfer agents can be used individually or in combination of two or more.

[0127] Furthermore, the content of the thiol-based chain transfer agent is preferably 0.1 to 2 parts by mass, and more preferably 0.2 to 1 part by mass, per 100 parts by mass of the coloring agent. Within this range, the effect of the chain transfer agent is enhanced, resulting in improved sensitivity, tapered shape, wrinkles, film shrinkage, and other properties.

[0128] <Polymerization inhibitor (H)> The photosensitive colored composition of the present invention may contain a polymerization inhibitor to prevent photosensitivity due to diffracted light from the mask during exposure. By adding a polymerization inhibitor, photosensitivity due to diffracted light from the mask during exposure in photolithography can be suppressed, making it easier to obtain patterns of the desired shape.

[0129] Polymerization inhibitors (H) include alkylcatechol compounds 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, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, and 2-n-butylcatechol. Examples include alkylresorcinol compounds such as cyrrresorcinol, 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 tripenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphine and trisnonylphenylphosphine; pyrogallol and phloroglucin.

[0130] The polymerization inhibitor (H) content is preferably 0.01 to 0.4 parts by mass of the nonvolatile content of the photosensitive coloring composition. Including an appropriate amount makes it easier to obtain a good pattern shape.

[0131] <UV absorber (I)> The photosensitive colored composition of the invention may contain an ultraviolet absorber (I). The ultraviolet absorber (I) in the present invention is an organic compound having an ultraviolet absorption function, and examples include benzotriazole organic compounds, triazine organic compounds, benzophenone organic compounds, salicylate organic compounds, cyanoacrylate organic compounds, and salicylate organic compounds.

[0132] The amount of UV absorber (I) is preferably 5 to 70% by mass of the total mass of the photopolymerization initiator and UV absorber. Including an appropriate amount further improves the resolution after development.

[0133] Furthermore, the total content of the photopolymerization initiator (D) and the ultraviolet absorber (I) is preferably 1 to 20% by mass of the nonvolatile content of the photosensitive colored composition. Including an appropriate amount further improves the adhesion between the substrate and the film, resulting in good resolution.

[0134] Benzotriazole organic compounds include 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, and 2-[2-hydroxy-3,5-bis(α, α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2′hydroxy-5′-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, a mixture of 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy,C7-9 side chain and linear alkyl ester, 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 Reaction product of 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t- Examples include butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole-2-yl)phenyl]propionate. Other oligomeric and polymer-type compounds having a benzotriazole structure can also be used.

[0135] More specifically, examples include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 from BASF Corporation; ADEKA LA-29, LA-31RG, LA-32, and LA-36 from ADEKA Corporation; KEMISORB 71, 73, 74, 79, and 279 from Chemipro Chemical Co., Ltd.; and RUVA-93 from Otsuka Chemical Co., Ltd.

[0136] Examples of triazine-based organic compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Products include 2,4-bis"2-hydroxy-4-butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine. Other oligomeric and polymeric compounds having a triazine structure can also be used.

[0137] More specifically, examples include KEMISORB 102 from Chemipro Chemical Co., Ltd., TINUVIN 400, 405, 460, 477, 479, and 1577ED from BASF, ADEKA LA-46 and LA-F70 from ADEKA Corporation, and CYASORB UV-1164 from Sun Chemical Co., Ltd.

[0138] Examples of benzophenone-based organic compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3-water, 2-hydroxy-4-n-octoxybenzophenone, 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, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone. Other oligomeric and polymer-type compounds having a benzophenone structure can also be used.

[0139] More specifically, examples include KEMISORB 10, 11, 11S, 12, and 111 from Chemipro Chemical Co., Ltd., SEESORB 101 and 107 from Cipro Chemical Co., Ltd., ADEKA Stab 1413 from ADEKA Corporation, and UV-12 from Sun Chemical Co., Ltd.

[0140] Examples of salicylic acid ester organic compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate. Other oligomeric and polymeric compounds having a salicylic acid ester structure can also be used.

[0141] <Antioxidant (J)> Photosensitive colored compositions may contain antioxidants. Antioxidants prevent the film formed from the photosensitive colored composition from yellowing due to oxidation during thermal processes such as heat curing and ITO annealing, and suppress the decrease in the film's transmittance. In particular, when the colorant concentration of the photosensitive colored composition is high, the content of photopolymerizable compound (D) decreases relatively, so increasing the amount of photopolymerization initiator or adding thermosetting compounds can easily cause the film to yellow. Therefore, including antioxidants can prevent yellowing due to oxidation during the heating process and suppress the decrease in the film's transmittance.

[0142] Antioxidant (J) is a compound having radical scavenging or peroxide decomposition functions. Examples of antioxidants include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, and hydroxylamine compounds. It is preferable that the antioxidant is a compound that does not contain halogen atoms.

[0143] Examples of hindered phenol antioxidants include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] Undecane, 1,3,5-Tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-Tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-Methylenebis(6-t-butyl-4-ethylphenol), 2,2'-Thiodiethylbis-(3,5-di- t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), i-octyl3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4, 6-Bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-Hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-Bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, Examples include 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethylphenol), 2,2'-methylene-bis-(6-(1-methylcyclohexyl)-p-cresol), and 2,4-dimethyl-6-(1-methylcyclohexyl)-phenol. Other oligomeric and polymer-type compounds having a hindered phenol structure can also be used.

[0144] More specifically, examples include ADEKA stubs AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 from ADEKA Corporation; KEMINOX 101, 179, 76, and 9425 from Chemipro Corporation; IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 from BASF Corporation; and Cyanox CY-1790 and CY-2777 from Sun Chemical Co., Ltd.

[0145] Examples of hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidine-4-yl)carbonate, and 1,2,2,6,6-penta Methyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-pi Ester of peridineethanol and 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazine-2-yl]-4,7-diazadecane-1,10-diamine, reaction product of bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) decandioate, 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyriperidyl)[[3,5-bi (1,1-dimethylethyl)-4-hydroxyphenyl]methyl]butylmalonatemethyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid ester, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,Examples include 6-hexamethylenediamine and 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide. Other oligomeric and polymeric compounds having a hindered amine structure can also be used.

[0146] Commercially available hindered amine antioxidants include ADEKA's Adekastab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP; Chemipro Chemical's KAMISTAB29, 62, 77, 94; BASF Japan's Tinuvin249, TINUVIN111FDL, 123, 144, 292, 5100; and Sun Chemical's Siasorb UV-3346, UV-3529, UV-3853.

[0147] Phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl) phosphite, tris(nonylphenyl) phosphite, tetra(C12~C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, and diphenyl mono(2 -Ethylhexyl) phosphite, diphenylisodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphonate, tris(tridecyl) phosphite, phenylisooctyl phosphite, phenylisodecyl phosphite, phenyldi(tridecyl) phosphite, diphenylisooctyl phosphite, diphenyltridecyl phosphite, 4,4'-isopropylide Diphenolalkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl Examples include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butanetriphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphitediethyl ester, sodium bis(4-t-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)benzene, and ethylbis(2,4-ditert-butyl-6-methylphenyl) phosphite. Other oligomer and polymer type compounds having a phosphite structure can also be used.

[0148] Commercially available phosphorus-based antioxidants include ADEKA's ADEKA Stab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP; BASF Japan's IRGAFOS168; and Clariant Chemicals' Hostanox P-EPQ.

[0149] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3'-thiobispropionate ditridecyl, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol. Other oligomeric and polymer-type compounds having a thioether structure can also be used.

[0150] Commercially available sulfur-based antioxidants include ADEKA's ADEKA Stab AO-412S and AO-503, and KEMINOXPLS from Chemipro Chemical Co., Ltd.

[0151] Antioxidants can be used individually or in combination of two or more types.

[0152] The antioxidant content is preferably 0.5 to 5.0% by mass of 100% by mass of the non-volatile content of the photosensitive coloring composition. An appropriate amount improves transmittance, spectral characteristics, and sensitivity.

[0153] <Leveling agent (K)> In order to improve the coatability of the composition on a transparent substrate and the drying properties of the colored film, it is preferable to add a leveling agent to the photosensitive colored composition of the present invention. Various surfactants such as silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants can be used as leveling agents.

[0154] Examples of silicone-based surfactants include linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0155] Commercially available products include BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345 / 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 from Big Chemie, and FZ-7002, 2110, 2 from Toray Dow Corning. Examples include 122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

[0156] Examples of fluorine-based surfactants include surfactants or leveling agents having fluorocarbon chains.

[0157] Commercially available products include AGC Seimi Chemical's Surflon S-242, S-243, S-420, S-611, S-651, S-386; DIC's Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS-21; Sumitomo 3M's FC-4430, FC-4432; Mitsubishi Materials Electronic Chemicals' EF-PP31N09, EF-PP33G1, EF-PP32C1; and Neos's Futergent 602A.

[0158] Nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristelle ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tripenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. Examples include sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkylimidazoline, etc.

[0159] More specifically, Kao's Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS -110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L1 06, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amito 102, 10 Examples include 5, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic® L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA Corporation, and (meth)acrylic acid-based (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0160] Cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

[0161] More specifically, examples include Kao Corporation's Acetamine 24, Cortamin 24P, 60W, and 86P Concentrate.

[0162] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfate, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyl ether disulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate esters.

[0163] More specifically, examples include Neos Co., Ltd.'s Futergent 100 and 150, and ADEKA Corporation's Adeka Hope YES-25, Adeka Call TS-230E, PS-440E, EC-8600, etc.

[0164] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkylamine oxides such as lauryldimethylamine oxide.

[0165] More specifically, examples include Kao Corporation's Anchitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N.

[0166] When the photosensitive colored composition of the present invention contains a surfactant, the amount of surfactant added is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, relative to the total non-volatile content of the composition of the present invention. Within this range, a good balance is achieved between the applicability, pattern adhesion, and transmittance of the colored composition. The photosensitive coloring composition of the present invention may contain only one type of surfactant or two or more types. If two or more types are included, it is preferable that their total amount be within the above range.

[0167] <Storage stabilizer (L)> The colored composition of the present invention may contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of storage stabilizers include benzyl trimethyl chloride, quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butyl pyrocatechol, tetraethylphosphine, and tetraphenylphosphine, and phosphates. The storage stabilizer can be used in an amount of 0.1 to 10% by mass, based on the total amount of the colorant (100% by mass).

[0168] <Adhesion enhancer (M)> The photosensitive colored composition of the present invention may contain adhesion-enhancing agents such as silane coupling agents to improve adhesion to the substrate. Improved adhesion due to the adhesion-enhancing agent results in better reproduction of fine lines and improved resolution.

[0169] Adhesion enhancers (M) include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane, epoxysilanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, and N-2-(aminoethyl)- Examples of silane coupling agents include aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and hydrochloride salts of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatetopropyltriethoxysilane. The adhesion enhancer can be used in an amount of 0.01 to 10 parts by mass, preferably 0.05 to 5 parts by mass, per 100 parts by mass of the coloring agent in the coloring composition. This range is preferable because it provides a greater effect and a good balance of adhesion, resolution, and sensitivity.

[0170] <Method for producing a photosensitive colored composition> A photosensitive colored composition can be produced by, for example, dispersing a colorant (A), a dispersion resin (B1), etc. to create a colorant dispersion. Then, the colorant dispersion, an alkali-soluble resin (B2), a polymerizable compound (C), and a photopolymerization initiator (D), etc., are blended and mixed. The blending materials and the timing of blending are arbitrary. Furthermore, the dispersion process can be performed multiple times.

[0171] The aforementioned dispersion process can be carried out using a dispersion device such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor.

[0172] <Removal of coarse particles> The photosensitive colored composition of the present invention is preferably subjected to the removal of coarse particles of 5 μm or larger, preferably 1 μm or larger, and more preferably 0.5 μm or larger, as well as any impurities, by means of centrifugal separation, filtration using a sintered filter or a membrane filter. Thus, the colored composition is preferably substantially free of particles of 0.5 μm or larger. More preferably, the particles are 0.3 μm or smaller.

[0173] <Moisture content in photosensitive colored composition> The photosensitive colored composition of the present invention preferably contains 2% by mass or less of water.

[0174] If the water content of the photosensitive coloring composition is within the above range, it exhibits excellent dispersion stability and sensitivity even after storage over time.

[0175] The water content in the photosensitive colored composition is preferably 1.8% by mass or less, and more preferably 1.6% by mass or less. If the water content is sufficiently low within this range, problems with dispersion stability and sensitivity are unlikely to occur even after storage over time.

[0176] There are no particular restrictions on the method for controlling the water content, and known methods can be used. For example, methods include manufacturing the photosensitive colored composition while blowing in a dry inert gas, or adding molecular sieves after manufacturing to dehydrate the mixture. Among these, the method of manufacturing while blowing in a dry inert gas is preferred.

[0177] The water content can be measured by known methods such as the Karl Fischer method.

[0178] <Amount of toluene in photosensitive colored composition> The photosensitive coloring composition of the present invention may contain toluene, and if so, the toluene content is preferably 0.1 to 10 ppm by mass. The upper limit of the toluene content is preferably 9 ppm by mass or less, more preferably 8 ppm by mass or less, and even more preferably 7 ppm by mass or less. The lower limit is preferably 0.2 ppm by mass or more, more preferably 0.3 ppm by mass or more, and even more preferably 0.4 ppm by mass or more.

[0179] <Color Filter> The color filter of the present invention preferably has filter segments formed from a photosensitive colored composition. The color filter preferably has red, green, and blue filter segments by appropriately selecting the type of colorant (A) used. Alternatively, the color filter may have complementary magenta, cyan, and yellow filter segments instead of these color filter segments. A reflective substrate can be used instead of a transparent substrate. A transparent substrate is, for example, a glass substrate. A reflective substrate is, for example, a substrate using aluminum electrodes or a thin metal film as the reflective surface. Each color filter can form a color filter segment with high color separation by reducing transmission outside the wavelength range of the target color, thereby suppressing mixing with other colors. For example, with a blue color filter, it is preferable to reduce the transmittance of wavelengths in the visible range other than around 380-490 nm. Similarly, with a green color filter, it is preferable to reduce the transmittance of wavelengths in the visible range other than around 490-590 nm. Furthermore, taking a red color filter as an example, it is preferable to have low transmittance at wavelengths in the visible range other than around 590-780 nm. In order to improve color separation between each color filter, the minimum transmittance of each color filter in the 380-780 nm range is preferably less than 2.5%, and most preferably less than 1.0%.

[0180] <How to manufacture color filters> In color filters, it is preferable to first form a black matrix on the substrate, and then form the filter segments. Alternatively, thin-film transistors (TFTs) can be formed on the substrate beforehand, and then the black matrix can be formed. Examples of black matrices include multilayer films of chromium or chromium / chromium oxide, inorganic films such as titanium nitride, and resin films in which light-shielding agents are dispersed.

[0181] Filter segments can be fabricated by methods such as printing, electrodeposition, transfer, inkjet, and photolithography. This specification describes the most preferred method: photolithography.

[0182] Photolithography involves, for example, applying a photosensitive colored composition containing a colorant of a certain tone onto a transparent substrate to form a film with a dry film thickness of approximately 0.2 to 5 μm. The resulting film (hereinafter referred to as the first film) is exposed (irradiated with light) through a mask having a predetermined pattern. Next, development is performed by immersion in a solvent or alkaline developer or by spraying the developer, removing uncured portions and obtaining the desired pattern. By performing this process similarly with photosensitive colored compositions containing colorants of other tones, color filters having filter segments of each color can be manufactured. Furthermore, a second film (oxygen barrier film) can be formed on the first film before exposure using polyvinyl alcohol or a water-soluble acrylic resin. This prevents the first film from coming into contact with oxygen, thus improving its exposure sensitivity. Additionally, the color filter can be heated to cure any uncured photopolymerizable compounds in the filter segments.

[0183] Coating equipment includes, for example, spray coating, spin coating, slit coating, and roll coating. A drying process can be performed during coating. Drying equipment includes, for example, a hot air oven and an infrared heater.

[0184] The developer can be an alkaline developer, for example, an inorganic alkali such as sodium carbonate or sodium hydroxide; or an organic alkali such as dimethylbenzylamine or triethanolamine. Furthermore, the developer may contain defoaming agents or surfactants.

[0185] The color filter of the present invention is bonded to a counter substrate using a sealant, liquid crystal is injected through an injection port provided in the sealed portion, the injection port is sealed, and a polarizing film or phase difference film is bonded to the outside of the substrate as needed to manufacture a color liquid crystal display device. This color liquid crystal display device can be used in liquid crystal display modes that perform colorization using color filters such as twisted nematic (TN), super-twisted nematic (STN), in-plane switching (IPS), vertically aligned (VA), and optically convened bend (OCB).

[0186] In this specification, color filters can be used in applications other than liquid crystal displays, such as solid-state image sensors, organic EL displays, quantum dot displays, electronic paper, and head-mounted displays.

[0187] <Solid-state image sensor> The solid-state image sensor of the present invention includes a color filter. One example of an embodiment used in a solid-state image sensor is an embodiment in which a substrate has a plurality of photodiodes that constitute the light-receiving area of ​​a solid-state image sensor (CCD image sensor, CMOS image sensor, or organic CMOS image sensor, etc.), and a light-receiving element made of polysilicon or the like, and the color filter of the present invention is provided on the side of the light-receiving element formation surface or on the opposite side of the formation surface.

[0188] <Liquid crystal display device> The image display device described herein includes a color filter. Preferably, the image display device further includes a light source. A liquid crystal display device is described as an example of an image display device. A liquid crystal display device comprises a color filter and a light source. Examples of light sources include cold cathode fluorescent lamps (CCFLs) and white LEDs, but in the present invention, it is preferable to use a white LED because it expands the red color reproduction range. Figure 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with the color filter of the present invention. The device 10 shown in Figure 1 comprises a pair of transparent substrates 11 and 21 arranged spaced apart and facing each other, with liquid crystal LC sealed between them.

[0189] Liquid crystal (LC) is oriented according to the driving mode, such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), and OCB (Optically Compensated Birefringence). A TFT (Thin Film Transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed on top of it. An alignment layer 14 is provided on top of the transparent electrode layer 13. In addition, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0190] 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).

[0191] A transparent protective film (not shown) is formed over the color filter 22 as needed, and a transparent electrode layer 23 made of, for example, ITO is formed on top of that, and an alignment layer 24 is provided covering the transparent electrode layer 23.

[0192] Furthermore, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. A backlight unit 30 is provided below the polarizing plate 15.

[0193] White LED light sources include those with a fluorescent filter formed on the surface of a blue LED, and those with a phosphor contained in the resin package of a blue LED. They have a wavelength (λ3) in which the emission intensity is maximum in the range of 430nm to 485nm, a wavelength (λ4) in which the emission intensity is maximum in the range of 530nm to 580nm, and a wavelength (λ5) in which the emission intensity is maximum in the range of 600nm to 650nm, and the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 (I4 / I3) is between 0.2 and 0.4. Preferably, a white LED light source (LED1) has spectral characteristics in which the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 (I5 / I3) is 0.1 or more and 1.3 or less, or a white LED light source (LED2) has spectral characteristics in which the wavelength (λ1) at which the emission intensity is maximum is in the range of 430 nm to 485 nm, the peak wavelength (λ2) of the second emission intensity is in the range of 530 nm to 580 nm, and the ratio of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 (I2 / I1) is 0.2 or more and 0.7 or less.

[0194] Examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

[0195] Examples of LED2 include the NSSW440 (manufactured by Nichia Corporation) and the NSSW304D (manufactured by Nichia Corporation). [Examples]

[0196] The present invention will be described below with reference to examples. In the examples, "parts" and "%" refer to "parts by mass" and "mass%", respectively.

[0197] The weight-average molecular weight (Mw), number-average molecular weight (Mn), acid value (mgKOH / g), amine value (mgKOH / g), and ammonium salt value (mgKOH / g) for resins such as resin (B) and resins used to produce dyes are as follows.

[0198] <Non-volatile content, Non-volatile content concentration> In this invention, non-volatile content refers to the mass residue after standing in an oven at 200°C for 30 minutes.

[0199] <Weight average molecular weight (Mw), number average molecular weight (Mn)> The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with a radioisotope detector. An HLC-8220GPC (Tosoh Corporation) was used, with two separation columns connected in series. Both columns were packed with two TSK-GEL SUPER HZM-N columns. Measurements were performed at an oven temperature of 40°C, using THF solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent, and 20 microliters were injected. All molecular weights are polystyrene equivalents.

[0200] <Acid value (mgKOH / g)> 0.5 to 1 g of resin solution was mixed with 80 ml of acetone and 10 ml of water and stirred to dissolve uniformly. A 0.1 mol / L aqueous KOH solution was used as the titrant, and the solution was titrated using an automatic titrator ("COM-555," manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mgKOH / g) of the resin solution. The acid value per unit of non-volatile content of the resin was then calculated from the acid value of the resin solution and the concentration of non-volatile content of the resin solution.

[0201] <Ammonium salt value (mgKOH / g)> The ammonium salt value is determined by titrating with a 0.1N silver nitrate solution using a 5% potassium chromate aqueous solution as an indicator, and then converted to the equivalent amount of potassium hydroxide. This value represents the ammonium salt value of the non-volatile portion.

[0202] <Micronization of coloring agent (A)> (Coloring agent (A-1)) 100 parts of CI Pigment Red 254 (BASF Japan's "Irgafore Red B-CF"), 10 parts of pigment derivative (b-1), 1000 parts of crushed salt, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 8 hours. This mixture was added to 2000 parts of warm water and stirred in a high-speed mixer for about 1 hour while being heated to about 80°C to form a slurry. After repeated filtration and washing to remove salt and solvent, it was dried at 80°C for 24 hours to obtain coloring agent (A-1).

[0203] (Coloring agent (A-2)) 500 parts of CI Pigment Red 177 ("Chromophthal Red A2B" manufactured by BASF Japan), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 120°C for 8 hours. Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to obtain coloring agent (A-2).

[0204] (Coloring agent (A-3)) 100 parts of CI Pigment Red 272 (BASF Japan's "Irgazin(r) Flame Red K 3800"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 10 hours. Next, this mixture was added to 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80°C to form a slurry. After repeated filtration and washing to remove sodium chloride and solvent, it was dried at 80°C for 24 hours to obtain coloring agent (A-3).

[0205] (Coloring agent (A-4)) 100 parts of CI Pigment Red 269 (Clariant's "Toner Magenta F8B"), 800 parts of sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 5 hours. 4000 parts of this mixture were added to warm water and stirred in a high-speed mixer for about 1 hour while heating to approximately 80°C to form a slurry. After repeated filtration and washing to remove salt and solvent, the mixture was dried at 80°C for 24 hours to obtain coloring agent (A-4).

[0206] (Coloring agent (A-5)) 100 parts of CI Pigment Green 58 (DIC Corporation's "FASTGEN GREEN A110"), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 6 hours. This mixture was added to 3000 parts of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to obtain 97 parts of coloring agent (A-5).

[0207] (Coloring agent (A-6)) 500 parts of CI Pigment Green 36 (Toyo Color Co., Ltd. "Lionol Green 6YK"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 120°C for 4 hours. Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to obtain 490 parts of coloring agent (A-6).

[0208] (Coloring agent (A-7)) 500 parts of CI Pigment Green 63 (Toyo Color Co., Ltd. "OPTLION GREEN 8885"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 120°C for 4 hours. Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to obtain 490 parts of coloring agent (A-7).

[0209] (Coloring agent (A-8)) 100 parts of CI Pigment Blue 15:6 (Toyo Color Co., Ltd. "Lionol Blue ES"), 1000 parts of crushed salt, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 50°C for 12 hours. This mixture was added to 3000 parts of warm water and stirred in a high-speed mixer for about 1 hour while heating to about 70°C to form a slurry. After repeated filtration and washing to remove salt and solvent, it was dried at 80°C for 24 hours to obtain coloring agent (A-8). (Coloring agent (A-9)) 100 parts of CI Pigment Yellow 138 (BASF Japan's "Paliotoll Yellow K0961HD"), 800 parts of crushed salt, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 4 hours. 3000 parts of this mixture were added to warm water and stirred in a high-speed mixer for about 1 hour while heating to approximately 80°C to form a slurry. After repeated filtration and washing to remove salt and solvent, the mixture was dried at 80°C for 24 hours to obtain coloring agent (A-9).

[0210] (Coloring agent (A-10)) 100 parts of CI Pigment Yellow 139 (BASF Japan's "Irgafore Yellow 2R-CF"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 10 hours. Next, this mixture was added to 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80°C to form a slurry. After repeated filtration and washing to remove sodium chloride and solvent, it was dried at 80°C for 24 hours to obtain the coloring agent (A-10).

[0211] (Coloring agent (A-11)) 100 parts of CI Pigment Yellow 150 (LANXESS "Yellow Pigment E4GN"), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 60°C for 10 hours. Next, this mixture was added to 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80°C to form a slurry. After repeated filtration and washing to remove sodium chloride and solvent, it was dried at 80°C for 24 hours to obtain coloring agent (A-11).

[0212] (Coloring agent (A-12)) 500 parts of CI Pigment Yellow 185 (BASF Japan's "Paliotoll Yellow D1155"), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 120°C for 8 hours. Next, this mixture was added to 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight to obtain the coloring agent (A-12).

[0213] (Coloring agent (A-13)) 300 parts of dioxazine-based purple pigment Pigment Violet 23 (Toyo Color Co., Ltd. "Lionogen Violet RL") were added to 3000 parts of 96% sulfuric acid and stirred for 1 hour, then poured into water at 5°C. After stirring for 1 hour, the mixture was filtered, washed with warm water until the washing solution was neutral, and dried at 70°C. 120 parts of the resulting acid-pasted pigment, 5 parts of pigment derivative (b-2), 1500 parts of pulverized sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 20 hours. This mixture was added to 5000 parts of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 70°C to form a slurry. After repeated filtration and washing with water to remove sodium chloride and solvent, the mixture was dried at 80°C for 24 hours to obtain pigment (A-13).

[0214] <Dye solution (a-1~3)> (A resin solution with cationic groups in its side chains) 67.3 parts of methyl ethyl ketone were charged into a four-necked separable flask equipped with a thermometer, stirrer, distillation tube, and condenser, and the temperature was raised to 75°C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were homogenized and then placed in a dropping funnel, which was attached to the four-necked separable flask, and added dropwise over 2 hours. Two hours after the end of the dropwise addition, it was confirmed that the polymerization yield was 98% or higher based on the non-volatile content, and the weight-average molecular weight (Mw) was 6830, and the mixture was cooled to 50°C. To this, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, and the mixture was reacted at 50°C for 2 hours. Then, the temperature was increased to 80°C over 1 hour, and the mixture was reacted for another 2 hours. In this way, a solution of resin 1 was obtained in which the resin component consisted of 47% by mass of ammonium groups and had cationic groups in the side chains. The ammonium salt value of the obtained resin 1 was 34 mgKOH / g.

[0215] (dye 1) 30 parts of resin 1 having cationic groups in its side chains (calculated as non-volatile content) were added to 2000 parts of water, and after thorough stirring and 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 was added dropwise to the resin solution. After addition, the mixture was stirred at 60°C for 120 minutes to allow the reaction to proceed. To confirm the endpoint of the reaction, the reaction solution was dropped onto filter paper, and the point at which the bleeding stopped was considered the endpoint, indicating that a salt-forming compound had been obtained. After cooling to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried in a dryer to remove moisture, thereby obtaining a coloring agent (dye 1), which is a salt-forming compound of CI Acid Red 52 and resin 1 having cationic groups in its side chains. At this time, the content of the active pigment component derived from CI Acid Red 52 in the coloring agent (dye 1) was 25% by mass.

[0216] (dye 2) The process was carried out in the same manner as for the production of colorant (dye 1), except that CI Acid Red 52 was replaced with CI Acid Red 289, to obtain a colorant (dye 2), which is a salt-forming compound of CI Acid Red 289 and resin 1 having a cationic group in its side chain. At this time, the content of the active pigment component derived from CI Acid Red 289 in the colorant (dye 2) was 27% by mass.

[0217] (dye 3) In a 1-liter stainless steel reaction vessel equipped with a reflux tube, 5.0 parts of CI Basic Violet 10 (BV10: Taoka Chemical Co., Ltd.: Rodamine B) and 1.6 parts of hydroxyethyl methacrylate (HEMA) were dissolved in 40 ml of dichloromethane under a nitrogen atmosphere. 2.2 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 0.25 parts of dimethylaminopyridine were added, and the mixture was stirred at room temperature for 24 hours. The resulting dichloromethane solution was washed with water, dried under reduced pressure, and then purified using a silica gel column to obtain a coloring agent (dye 3).

[0218] (Preparation of dye solution (a-1)) The following mixtures were stirred and mixed until homogeneous, and then filtered through a 5.0 μm pore size filter to prepare a colored composition (dye solution (a-1)). Coloring agent (dye 1) 12.5 parts Propylene glycol monomethyl ether acetate 87.5 parts In the following, propylene glycol monomethyl ether acetate may be referred to as PGMAc.

[0219] (Preparation of dye solutions (a-2) and (a-3)) Dye solutions (a-2) and (a-3) were prepared in the same manner as dye solution (a-1) using colorants (dye 2 and dye 3).

[0220] (Dye derivative (b)) The structures of each dye derivative used (b-1 to b-4) are shown below.

[0221] [ka] JPEG2026098942000009.jpg4375JPEG2026098942000010.jpg65110JPEG2026098942000011.jpg50119

[0222] (Preparation of dispersion resin (B1-1) solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 108 parts of 3-mercapto-1,2-propanediol, 174 parts of pyromellitic dianhydride, 650 parts of propylene glycol monomethyl ether acetate, and 0.2 parts of monobutyltin oxide as a catalyst were charged. After purging with nitrogen gas, the mixture was reacted at 120°C for 5 hours (first step). Acid value measurement confirmed that more than 95% of the acid anhydride groups were half-esterified. Next, 160 parts of the compound obtained in the first step (based on non-volatile content), 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl methacrylate, 50 parts of methacrylic acid, and 663 parts of propylene glycol monomethyl ether acetate were charged. The reaction vessel was heated to 80°C, and 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were added, and the mixture was reacted for 12 hours (second step). Non-volatile content measurement confirmed that 95% had reacted. Finally, 500 parts of a 50% propylene glycol monomethyl ether acetate solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were charged, and IR measurement showed 2270 cm⁻¹ based on the isocyanate group. -1 The reaction was carried out until the peak disappeared (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the non-volatile content was adjusted with propylene glycol monomethyl ether acetate to obtain a dispersion resin (B1-1) solution with a non-volatile content of 40%. The acid value of the obtained dispersion resin (B1-1) was 68, the unsaturated double bond equivalent was 1593, and the weight-average molecular weight was 13000.

[0223] (Preparation of dispersion resin (B1-2) solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 80 parts n-butyl acrylate, 60 parts methyl methacrylate, 20 parts methacrylic acid, 20 parts Karenz MOI-BM (Showa Denko), 20 parts ETERNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate, Ube Industries), and 100 parts propylene glycol monomethyl ether acetate were charged and the mixture was purged with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 14 parts 2-mercapto-2-methyl-1,3-propanediol and 0.1 parts 2,2'-azobisisobutyronitrile was added, and the mixture was reacted for 10 hours. Non-volatile content measurement confirmed that 95% of the mixture had reacted. Next, 39 parts of BPAF:9,9-bis(3,4-dicarboxyphenyl)fluorendiohydride (manufactured by JFE Chemical Corporation), 106 parts of C-1015N (bifunctional polycarbonate polyol, trade name Kuraray Polyol C-1015N (hydroxyl value 112 mg KOH / g, manufactured by Kuraray Co., Ltd.)), 33 parts of trimellitic anhydride, 392 parts of cyclohexanone, and 0.40 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 100°C for 7 hours. The reaction was terminated after confirming that more than 98% of the acid anhydrides had been half-esterified by measuring the acid value. The mixture was adjusted to a non-volatile content of 40% with propylene glycol monomethyl ether acetate to obtain a dispersion resin (B1-2) solution with an acid value of 94 mg KOH / g, a weight-average molecular weight of 25000, and no polymerizable unsaturated groups.

[0224] (Production of resin (B1-3) solution) In a reaction vessel equipped with a gas inlet pipe, temperature control, condenser, and stirrer, 10 parts methacrylic acid, 100 parts methyl methacrylate, 70 parts i-butyl methacrylate, 20 parts benzyl methacrylate, and 50 parts propylene glycol monomethyl ether acetate were charged, and the mixture was purged with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts of 3-mercapto-1,2-propanediol were added. The temperature was raised to 90°C, and the reaction was carried out for 7 hours while adding a solution of 0.1 parts of 2,2'-azobisisobutyronitrile added to 90 parts of propylene glycol monomethyl ether acetate. Non-volatile content measurement confirmed that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of propylene glycol monomethyl ether acetate, 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. After confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value, the reaction was terminated. Propylene glycol monomethyl ether acetate was added to dilute the solution to a non-volatile content of 40% by measuring the non-volatile content, yielding a dispersion resin (B1-3) solution with an acid value of 70 mg KOH / g, a weight-average molecular weight of 8500, and no polymerizable unsaturated groups.

[0225] (Production of resin (B1-4) solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 50.0 parts of t-butyl acrylate, 45.0 parts of methyl methacrylate, and 5.0 parts of methacrylic acid were charged, and the vessel was purged with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 70.7 parts of propylene glycol monomethyl ether acetate was added, and the mixture was reacted for 10 hours. Non-volatile content measurement confirmed that 95% of the mixture had reacted. Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 38.0 parts of propylene glycol monomethyl ether acetate, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120°C for 5 hours. Subsequently, 12.1 g of 3-methoxybutanol was added, and the mixture was reacted at 120°C for 3 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value. After the reaction was complete, propylene glycol monomethyl ether acetate was added to prepare a solution with an acid value of 110 mg KOH / g, a weight-average molecular weight of 9000, and no polymerizable unsaturated groups, resulting in a dispersion resin solution (B1-4).

[0226] (Production of resin (B1-5) solution) In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 20.0 parts of t-butyl acrylate, 45.0 parts of methyl methacrylate, 30.0 parts of ethyl acrylate, and 5.0 parts of methacrylic acid were charged, and the vessel was purged with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 6.0 parts of 3-mercapto-1,2-propanediol and 0.1 parts of 2,2'-azobisisobutyronitrile dissolved in 70.7 parts of propylene glycol monomethyl ether acetate was added, and the mixture was reacted for 10 hours. Non-volatile content measurement confirmed that 95% of the mixture had reacted. Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 38.0 parts of propylene glycol monomethyl ether acetate, and 0.2 parts of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120°C for 5 hours. Subsequently, 12.1 g of 3-methoxybutanol was added, and the mixture was reacted at 120°C for 3 hours. The reaction was terminated after confirming that more than 98% of the acid anhydride had been half-esterified by measuring the acid value. After the reaction was complete, propylene glycol monomethyl ether acetate was added to prepare a solution with an acid value of 105 mg KOH / g, a weight-average molecular weight of 9400, and no polymerizable unsaturated groups, resulting in a dispersion resin solution (B1-5).

[0227] <Preparation of colored composition> (Manufacturing of coloring compositions) [Manufacturing Example 1] After stirring and mixing the following mixture until homogeneous, it was dispersed for 3 hours using 0.5 mm diameter zirconia beads in an Eiger mill (Eiger Japan's "Mini Model M-250 MKII"), and then filtered through a 5.0 μm pore size filter to prepare a colored composition (X-1) with 20% by mass of nonvolatile components. Pigment (A-1) 15.0 parts Pigment derivative (b-1) 1.0 part Resin (B1-1) solution (40% non-volatile content) 10.0 parts Solvent (SM) 74.0 parts Furthermore, the solvent (SM) is prepared by mixing (S-1) to (S-6) below in the parts by mass indicated for each component. (S-1) PGMAc (boiling point 146℃) 20 parts (S-2) Cyclohexanone (boiling point 155°C) 20 parts (S-3)3-Ethoxypropionate ethyl (boiling point 169°C) 20 parts (S-4) Propylene glycol monomethyl ether (boiling point 121°C) 20 parts (S-5) Cyclohexanol acetate (boiling point 172°C) 10 parts (S-6) Dipropylene glycol methyl ether acetate (boiling point 188°C) 10 parts

[0228] [Manufacturing Examples 2-23] (Manufacturing of colored compositions (X-2~26)) Colored compositions (X-2 to X-26) were prepared in the same manner as colored composition (X-1), except that the composition was changed as shown in Table 1.

[0229] [Table 1]

[0230] [Example 1] (Photosensitive coloring composition (Y-1)) The following raw materials were mixed and stirred, and filtered through a 1.0 μm pore size filter to obtain a photosensitive colored composition (Y-1). Coloring composition (X-1) solution (non-volatile content: 20.0%): 65.0 parts Resin (B2-2-M) solution (non-volatile content: 40%): 1.0 part Polymerizable compound (C1-1) solution (non-volatile content: 60%): 3.3 parts Photoinitiator (D1-1-1): 0.4 part Solvent (S-M): 28.35 parts Others (total of the following raw materials): 1.95 parts Thermosetting compound solution (E-1): 0.24 part Thermosetting compound solution (E-2): 0.24 part Sensitizer (F): 0.05 part Thiol-based chain transfer agent (G): 0.19 part Polymerization inhibitor (H): 0.03 part UV absorber (I): 0.05 part Antioxidant (J): 0.05 part Surfactant (K: non-volatile content: 3%): 1.00 part Storage stabilizer (L): 0.05 part Adhesion improver (M): 0.05 part

[0231] [Examples 2 to 52, Comparative Examples 1 and 2] (Photosensitive coloring composition (Y-2 to 54)) Except for changing to the compositions and blending amounts (parts by mass) shown in Tables 2 to 7, in the same manner as the photosensitive coloring composition (Y-1), after stirring and mixing the mixture to be uniform, it was filtered through a filter with a pore size of 1.0 μm to obtain the photosensitive coloring compositions (Y-2 to 54). Details of each component used in Tables 2 to 7 are as follows.

[0232] [Production of the mixture of an alkali-soluble resin (B2-1-M: non-photosensitive resin)] [Preparation of an alkali-soluble resin (B2-1-1) solution] A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer into a separable four-neck flask. 196 parts of propylene glycol monomethyl ether acetate were charged into the vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 37.2 parts n-butyl methacrylate, 12.9 parts 2-hydroxyethyl methacrylate, 12.0 parts methacrylic acid, 20.7 parts paracumylphenol ethylene oxide modified acrylate (Toagosei Co., Ltd. "Aronics M110"), and 1.1 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the dropwise addition was complete, the reaction was continued for another 3 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately two parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was then added to the previously synthesized resin solution to prepare an alkali-soluble resin (B2-1-1) solution with a non-volatile content of 40%. The weight-average molecular weight (Mw) was 26,000.

[0233] (Preparation of alkali-soluble resin (B2-1-2) solution) A flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube was subjected to a nitrogen atmosphere. 210 parts of propylene glycol monomethyl ether acetate were added, and the temperature was raised to 100°C while stirring. Next, 106 parts of benzyl methacrylate, 22 parts of acrylic acid, and 22 parts of dicyclopentanyl methacrylate (FA-513M, Hitachi Chemical Co., Ltd.) were dissolved in 215 parts of propylene glycol monomethyl ether acetate. A solution prepared by dissolving 3.6 parts of 2,2'-azobisisobutyronitrile was then added dropwise to the flask, and the mixture was stirred at 100°C for 5 hours to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was then added to the previously synthesized resin solution to adjust the non-volatile content to 40%, thereby obtaining an alkali-soluble resin (B2-1-2) solution with a weight-average molecular weight (Mw) of 10,000.

[0234] (Preparation of alkali-soluble resin (B2-1-M) mixture) Alkali-soluble resin (B2-1-M) mixture was prepared by mixing and stirring equal amounts of alkali-soluble resin (B2-1-1) solution and alkali-soluble resin (B2-1-2) solution.

[0235] <Manufacturing of alkali-soluble resin (B2-2-M: photosensitive resin) mixture> (Preparation of alkali-soluble resin (B2-2-1) solution) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer into a separable four-neck flask. 207 parts of propylene glycol monomethyl ether acetate were charged into the vessel, and the temperature was raised to 80°C. After purging the reaction vessel with nitrogen, a mixture of 20 parts methacrylic acid, 20 parts paracumylphenol ethylene oxide-modified acrylate (Aronics M110, manufactured by Toagosei Co., Ltd.), 45 parts methyl methacrylate, 8.5 parts 2-hydroxyethyl methacrylate, and 1.33 parts 2,2'-azobisisobutyronitrile was added dropwise over 2 hours via the dropping tube. After the dropwise addition was complete, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, the entire copolymer solution was stirred while injecting dry air for 1 hour after stopping the nitrogen gas supply, and then cooled to room temperature. A mixture of 6.5 parts 2-methacryloyloxyethyl isocyanate (Kalenz MOI, Showa Denko Co., Ltd.), 0.08 parts dibutyltin laurate, and 26 parts propylene glycol monomethyl ether acetate was added dropwise at 70°C for 3 hours. After the dropwise addition was complete, the reaction was continued for another hour to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution were sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was then added to the previously synthesized resin solution to prepare an alkali-soluble resin (B2-2-1) with a non-volatile content of 40%. The weight-average molecular weight (Mw) of the alkali-soluble resin (B2-2-1) was 18,000, and the acid value was 130 mgKOH / g.

[0236] (Preparation of alkali-soluble resin (B2-2-2) solution) In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, 333 g of propylene glycol monomethyl ether acetate was introduced. After changing the atmosphere inside the flask from air to nitrogen, the temperature was raised to 100°C. A solution consisting of 70.5 g (0.40 mol) of benzyl methacrylate, 71.1 g (0.50 mol) of glycidyl methacrylate, 22.0 g (0.10 mol) of tricyclodecane skeleton monomethacrylate (FA-513M, Hitachi Chemical Co., Ltd.), and 164 g of propylene glycol monomethyl ether acetate, to which 3.6 g of azobisisobutyronitrile was added, was added dropwise to the flask from the dropping funnel over 2 hours, and the mixture was then stirred at 100°C for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 43.0 g of methacrylic acid [0.5 mol, (100 mol%) relative to the glycidyl groups of the glycidyl methacrylate used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone were added to the flask. The reaction was continued at 110°C for 6 hours until the non-volatile acid value reached 1 mg KOH / g, at which point the reaction was terminated. Next, 60.9 g (0.40 mol) of tetrahydrophthalic anhydride and 0.8 g of triethylamine were added, and the reaction was carried out at 120°C for 3.5 hours to obtain a photosensitive transparent resin solution with an acid value of 80 mg KOH / g. After cooling to room temperature, approximately 2 g of the photosensitive transparent resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was then added to the previously synthesized photosensitive transparent resin solution to prepare an alkali-soluble resin (B2-2-2) solution by reducing the non-volatile content to 40% by mass. The weight-average molecular weight (Mw) of the alkali-soluble resin (B2-2-2) was 12,000, and the acid value was 80 mgKOH / g.

[0237] (Preparation of alkali-soluble resin (B2-2-3) solution) In a flask equipped with a stirrer, thermometer, reflux condenser, dropping funnel, and nitrogen inlet tube, 182 g of propylene glycol monomethyl ether acetate was introduced. After changing the atmosphere inside the flask from air to nitrogen, the temperature was raised to 100°C. A solution consisting of 70.5 g (0.40 mol) of benzyl methacrylate, 43.0 g (0.5 mol) of methacrylic acid, 22.0 g (0.10 mol) of tricyclodecane skeleton monomethacrylate (FA-513M, Hitachi Chemical Co., Ltd.), and 136 g of propylene glycol monomethyl ether acetate, to which 3.6 g of azobisisobutyronitrile was added, was added dropwise to the flask from the dropping funnel over 2 hours, and the mixture was then stirred at 100°C for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 35.5 g [0.25 mol, (50 mol%) relative to the carboxyl groups of the methacrylic acid used in this reaction)], 0.9 g of trisdimethylaminomethylphenol, and 0.145 g of hydroquinone were added to the flask. The reaction was continued at 110°C for 6 hours to obtain a photosensitive transparent resin solution with an acid value of 79 mg KOH / g. After cooling to room temperature, approximately 2 g of the photosensitive transparent resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was then added to the previously synthesized photosensitive transparent resin solution to prepare an alkali-soluble resin (B2-2-3) solution by adding propylene glycol monomethyl ether acetate so that the non-volatile content was 40% by mass. The weight-average molecular weight (Mw) of the alkali-soluble resin (B2-2-3) was 13,000, and the acid value was 79 mg KOH / g.

[0238] (Preparation of alkali-soluble resin (B2-2-4) solution) A separable flask with a condenser was prepared as the reaction vessel. On the other hand, a monomer dropping vessel was prepared by thoroughly stirring and mixing 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, 120 parts of methyl methacrylate, 4 parts of t-butyl peroxy-2-ethylhexanoate ("Perbutyl O" manufactured by Nippon Oil & Fats Co., Ltd.), and 40 parts of propylene glycol monomethyl ether acetate. A chain transfer agent dropping vessel was prepared by thoroughly stirring and mixing 8 parts of n-dodecanethiol and 32 parts of propylene glycol monomethyl ether acetate. 395 parts of propylene glycol monomethyl ether acetate were charged into the reaction vessel, and after purging with nitrogen, the temperature of the reaction vessel was raised to 90°C by heating in an oil bath while stirring. After the temperature of the reaction vessel stabilized at 90°C, dropping was started from the monomer dropping vessel and the chain transfer agent dropping vessel. The addition was carried out dropwise over 135 minutes each, while maintaining the temperature at 90°C. Sixty minutes after the addition was completed, the temperature was raised to 110°C in the reaction vessel. After maintaining 110°C for 3 hours, a gas inlet tube was attached to the separable flask, and bubbling of an oxygen / nitrogen = 5 / 95 (volume ratio) mixed gas was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were charged into the reaction vessel, and the mixture was reacted at 110°C for 12 hours. After that, 150 parts of propylene glycol monomethyl ether acetate were added, and the mixture was cooled to room temperature. Approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl ether acetate was then added to the previously synthesized resin solution so that the non-volatile content was 40% by mass to obtain an alkali-soluble resin (B2-2-4) solution. The weight-average molecular weight (Mw) of the alkali-soluble resin (B2-2-4) was 18,000, and the acid value was 2 mgKOH / g.

[0239] (Preparation of alkali-soluble resin (B2-2-M) mixture) A resin mixture (B2-2-M) was prepared by mixing and stirring equal amounts of four types of alkali-soluble resins (B2-2-1) to (B2-2-4).

[0240] <Polymerizable compound (C)>

[0241] (Production of polymerizable compound (C1-1) solution) To 422 parts by mass of a tetrafunctional epoxy compound, Denacol EX-614B (manufactured by Nagase ChemteX), sorbitol polyglycidyl ether (epoxy equivalent 173 g / eq), 175 parts by mass of acrylic acid was added. Then, 397 parts by mass of propylene glycol monomethyl ether acetate, 3 parts by mass of triethylamine, and 0.6 parts of 4-methoxyphenol were added, and the mixture was heated to 120°C while blowing in oxygen, and the reaction was allowed to proceed for 8 hours. The reaction of acrylic acid was measured by oxidation, and it was confirmed that the reaction rate was 95% or higher. Finally, a polymerizable compound (C1-1) solution with a solid content of 60% and containing 6 secondary hydroxyl groups and 4 polymerizable unsaturated groups was obtained.

[0242] (Production of polymerizable compound (C1-2) liquid) To 416 parts by mass of a tetrafunctional epoxy compound, Denacol EX-614B (manufactured by Nagase ChemteX), sorbitol polyglycidyl ether, 130 parts by mass of acrylic acid and 52 parts by mass of methacrylic acid were added. Then, 399 parts by mass of propylene glycol monomethyl ether acetate, 3 parts by mass of triethylamine, and 0.6 parts by mass of 4-methoxyphenol were added, and the mixture was heated to 120°C while blowing in oxygen, and the reaction was allowed to proceed for 8 hours. The reaction between acrylic acid and methacrylic acid was confirmed by measuring the acid value, and a reaction rate of 95% or more was confirmed to be obtained, yielding a polymerizable compound (C1-2) solution with a solid content of 60%, containing 6 secondary hydroxyl groups and 4 polymerizable unsaturated groups.

[0243] (Preparation of polymerizable compound (C1-3) solution) To 410 parts by mass of a tetrafunctional epoxy compound, Denacol EX-614B (manufactured by Nagase ChemteX Corporation), sorbitol polyglycidyl ether, 85 parts by mass of acrylic acid and 102 parts by mass of methacrylic acid were added. 398 parts by mass of propylene glycol monomethyl ether acetate, 3 parts by mass of triethylamine and 0.6 parts by mass of 4-methoxyphenol were added, and while blowing oxygen, the mixture was heated to 120 °C and reacted for 8 hours. The reaction of acrylic acid and methacrylic acid was carried out by measuring the acid value, and it was confirmed that the reaction rate was 95% or more, thereby obtaining a polymerizable compound (C1-3) solution having 6 secondary hydroxyl groups and 4 polymerizable unsaturated groups with a solid content of 60%.

[0244] (Production of polymerizable compound (C1-4) solution) To 399 parts by mass of a tetrafunctional epoxy compound, Denacol EX-614B (manufactured by Nagase ChemteX Corporation), sorbitol polyglycidyl ether, 199 parts by mass of methacrylic acid was added. 398 parts by mass of propylene glycol monomethyl ether acetate, 3 parts by mass of triethylamine and 0.6 parts by mass of 4-methoxyphenol were added, and while blowing oxygen, the mixture was heated to 120 °C and reacted for 8 hours. The progress of the reaction of methacrylic acid was confirmed by measuring the acid value, and it was confirmed that the reaction rate was 95% or more, thereby obtaining a polymerizable compound (C1-4) solution having 6 secondary hydroxyl groups and 4 polymerizable unsaturated groups with a solid content of 60%.

[0245] (Production of polymerizable compound (C1-5) solution) To 418 parts by mass of a tetrafunctional epoxy compound, Denacol EX-512 (manufactured by Nagase ChemteX Corporation), polyglycerol polyglycidyl ether (epoxy equivalent (100.8 g / eq)), 179 parts by mass of acrylic acid was added. 398 parts by mass of propylene glycol monomethyl ether acetate, 3 parts by mass of triethylamine and 0.6 parts by mass of 4-methoxyphenol were added, and while blowing oxygen, the mixture was heated to 120 °C and reacted for 8 hours. The reaction of acrylic acid was carried out by measuring the acid value, thereby obtaining a polymerizable compound (C1-5) solution having 6 secondary hydroxyl groups and 4 polymerizable unsaturated groups with a solid content of 60%.

[0246] (Preparation of polymerizable compound (C1-6) solution) To 349 parts by mass of a trifunctional epoxy compound, trimethylolpropane triglycidyl ether epoxy equivalent (168 g / eq), 249 parts by mass of acrylic acid was added. Then, 398 parts by mass of propylene glycol monomethyl ether acetate, 3 parts by mass of triethylamine, and 0.6 parts by mass of 4-methoxyphenol were added, and the mixture was heated to 120°C while blowing in oxygen, and the reaction was allowed to proceed for 8 hours. The reaction with acrylic acid was determined by measuring the acid value, and a polymerizable compound (C1-6) solution with a solid content of 60% and containing three secondary hydroxyl groups and three polymerizable unsaturated groups was obtained.

[0247] (Preparation of polymerizable compound (C1-7) solution) 60 parts by mass of soybean oil-modified epoxy acrylate [EBECRYL860 (manufactured by Daicel Ornex)] and 40 parts by mass of propylene glycol monomethyl ether acetate were added and mixed to obtain a polymerizable compound (C1-7) solution with a solid content of 60%, containing four secondary hydroxyl groups and four polymerizable unsaturated groups.

[0248] (Preparation of polymerizable compound (C-2) solution) A mixture of dipentaerythritol pentaacrylate and dipentaerythritol hexaacrylate [Aronics M-402 (manufactured by Toagosei Co., Ltd.)] was mixed with 40 parts by mass of propylene glycol monomethyl ether acetate to obtain a polymerizable compound (C-2) solution with a solid content of 60%.

[0249] <Photopolymerization initiator (D)> (D-1)2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Omnirad 907 (manufactured by IGM Resins)] (D-2)2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Omnirad 379EG (manufactured by IGM Resins)] (D-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide [Omnirad TPO (manufactured by IGM Resins)] (D-4)2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole [Biimidazole (manufactured by Kurogane Kasei Co., Ltd.)] (D-5)p-dimethylaminoacetophenone [DMA (manufactured by Daikifine Co., Ltd.)] (D-6) Ethane-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl], 1-(O-acetyloxime) [Omnirad 2959 (manufactured by IGM Resins)] (D-7) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Omnirad 819 (manufactured by IGM Resins)] The above (D-1) to (D-7) were mixed in equal amounts to form a photopolymerization initiator (DM). (D1-1-1) An oxime ester-based photopolymerization initiator having a carbazole skeleton as shown in formula (2) below. Formula (2) [ka]

[0250] (D1-1-2) A mixture comprising equal amounts of the following four types of oxime ester photopolymerization initiators having a carbazole skeleton. [ka]

[0251] (D1-1-3) A mixture comprising equal amounts of three oxime ester-based photopolymerization initiators having the carbazole skeleton shown in formula (3) below. Formula (3) [ka]

[0252] (D1-2-1) An oxime ester-based photopolymerization initiator having a diphenyl skeleton as shown in formula (4) below. Formula (4) [ka]

[0253] (D1-2-2) An oxime ester-based photopolymerization initiator having a diphenyl skeleton as shown in formula (5) below. Formula (5) [ka] (D1-2-3) Oxime ester photopolymerization initiator having a diphenyl skeleton as shown in formula (6) below. Formula (6) [ka]

[0254] (D1-3) Oxime ester photopolymerization initiator having a fluorene skeleton as shown in formula (7) below. Formula (7) [ka]

[0255] (D1-4) An oxime ester-based photopolymerization initiator having two oxime ester groups as shown in formula (8) below. Formula (8) [ka]

[0256] <Thermosetting compound (E)> ·Thermosetting compound (E-1) (E-1-1) 1,2-epoxy-4-(2-oxyranyl)cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol [EHPE-3150 (manufactured by Daicel Corporation)] (E-1-2) Glycidyl etherified epoxy compound of sorbitol [Denacol EX611 (manufactured by Nagase ChemteX Corporation)] (E-1-3) Triglycidyl isocyanurate Equal amounts of (E-1-1) to (E-1-3) were mixed to form thermosetting compound (E-1). ·Thermosetting compound (E-2): 3-Ethyl-3-[(3-ethyloxetane-3-yl)methoxymethyl]oxetane [Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

[0257] <Sensitizer (F)> (F-1)2,4-Diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)] (F-2)4,4'-Bis(diethylamino)benzophenone [CHEMARK DEABP (manufactured by Chemark Chemical)] As described above, (F-1) and (F-2) were mixed in equal amounts to form the sensitizer (F).

[0258] <Thiol-based chain transfer agent (G)> (G-1) Trimethylolethantris(3-mercaptobutyrate) [TEMB (manufactured by Showa Denko)] (G-2) Trimethylolpropanetris(3-mercaptobutyrate) [TPMB (manufactured by Showa Denko)] (G-3) Pentaerythritol tetrakis(3-mercaptopropionate) [PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (G-4) Trimethylolpropanetris (3-mercaptopropionate) [TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (G-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)] The above (G-1) to (G-5) were mixed in equal amounts to form the thiol-based chain transfer agent (G).

[0259] <Polymerization inhibitor (H)> (H-1)3-methylcatechol (H-2)methylhydroquinone (H-3)tert-butylhydroquinone The above (H-1) to (H-3) were mixed in equal amounts to form polymerization inhibitor (H).

[0260] <UV absorber (I)> (I-1)2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine[TINUVIN400 (manufactured by BASF Japan)] (I-2)2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN900 (manufactured by BASF Japan)] As described above, (I-1) and (I-2) were mixed in equal amounts to obtain the ultraviolet absorber (I).

[0261] <Antioxidant (J)> (J-1) Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (J-2) 3,3′-Dioctadecyl Thiodipropanoate (J-3) Tris[2,4-di-(t)-butylphenyl]phosphine (J-4) Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (J-5) p-octylphenyl salicylate The above (J-1) to (J-5) were mixed in equal amounts to form antioxidant (J).

[0262] <Leveling agent (K)> One unit of "BYK-330" manufactured by Big Chemie Co., Ltd. One unit of DIC Corporation's "Megafuck F-551", and Kao Corporation's "Emulgen 103" (1 unit) A mixed solution obtained by dissolving PGMAc in 97 parts.

[0263] <Storage stabilizer (L)> (L-1)2,6-bis(1,1-dimethylethyl)-4-methylphenol (manufactured by Honshu Chemical Industry Co., Ltd. as "BHT") (L-2) Triphenylphosphine (manufactured by Hokko Chemical Industry Co., Ltd. as "TPP") The above (L-1) and (L-2) were mixed in equal amounts to form storage stabilizer (L).

[0264] <Adhesion enhancer (M)> (M-1) "KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.)" (M-2)3-Glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (M-3)3-Methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (M-4)N-2-(aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (M-5)3-mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)] The above (M-1) to (M-5) were mixed in equal amounts to form adhesion improver (M).

[0265] <Solvent (S)> The solvent (SM) is prepared by mixing (S-1) to (S-6) below in the parts by mass indicated for each. (S-1) PGMAc (boiling point 146℃) 20 parts (S-2) Cyclohexanone (boiling point 155°C) 20 parts (S-3)3-Ethoxypropionate ethyl (boiling point 169°C) 20 parts (S-4) Propylene glycol monomethyl ether (boiling point 121°C) 20 parts (S-5) Cyclohexanol acetate (boiling point 172°C) 10 parts (S-6) Dipropylene glycol methyl ether acetate (boiling point 188°C) 10 parts

[0266] <Evaluation of photosensitive colored compositions> The obtained photosensitive colored compositions (Y-1 to Y-54) were evaluated using the following method. The results are shown in Table 3.

[0267] <Pixel adhesion> The pixel adhesion of the obtained photosensitive colored compositions was evaluated using the following method. A photosensitive composition was applied to a 200 mm diameter silicon wafer substrate using a spin coater to a thickness of 0.50 μm after drying, and the substrate was dried at 100°C for 1 minute. Next, using an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon), exposure was performed at a wavelength of 365 nm and a density of 2000 J / m². 2 Exposure was performed. Exposure was carried out through a photomask having a 1.00 μm square aperture. The exposed film was paddle developed for 1 minute with TMAH 2.38% (a 2.38% aqueous solution of tetramethylammonium hydroxide, manufactured by Tama Chemical Industry Co., Ltd.). After paddle development, it was rinsed with pure water using a spin shower for 20 seconds and then spin-dried. The cross-sectional shape of the pixels formed by the aperture was observed using a scanning electron microscope (Hitachi High-Tech Corporation "S-3000N") and evaluated according to the following criteria. The percentage of pixel delamination occurring within the formed pixel pattern is ◎: Less than 10% (Excellent) ○: 10% or more, less than 20% (Good) △: 20% or more, less than 30% (usable) ×: 30% or more (Not practical)

[0268] <Pixel Rectangle> The pixel rectangularity of the obtained photosensitive colored compositions was evaluated using the following method. A photosensitive composition was applied to a 200 mm diameter silicon wafer substrate using a spin coater to a thickness of 0.50 μm after drying, and the substrate was dried at 100°C for 1 minute. Next, using an i-line stepper exposure system FPA-3000i5+ (manufactured by Canon), exposure was performed at a wavelength of 365 nm and a density of 2000 J / m². 2 Exposure was performed. Exposure was carried out through a photomask having a 1.00 μm square aperture. The exposed film was paddle developed for 1 minute with TMAH 2.38% (a 2.38% aqueous solution of tetramethylammonium hydroxide, manufactured by Tama Chemical Industry Co., Ltd.). After paddle development, it was rinsed with pure water using a spin shower for 20 seconds and then spin-dried. The cross-sectional shape of the pixels formed by the aperture was observed using a scanning electron microscope (Hitachi High-Tech Corporation "S-3000N") and evaluated according to the following criteria. The ratio of the upper base line width (T) of the formed pattern to the midpoint width (S) between the upper and lower bases, the T / S value, is ◎: 0.70 or higher (Excellent) ○: 0.65 or higher, less than 0.70 (good) △: 0.60 or higher, less than 0.65 (usable) ×: Less than 0.60 (Not practical)

[0269] <Evaluation of solvent resistance> A photosensitive colored composition for color filters was applied to a glass substrate using a slit die coater, and then pre-baked on a 90°C hot plate for 2 minutes to form a 1 μm thick coating. Next, after the substrate with the coating was cooled to room temperature, radiation including wavelengths of 365 nm, 405 nm, and 436 nm was applied to the coating at a rate of 1,000 J / m² using a high-pressure mercury lamp via a striped photomask. 2The substrate was exposed to the specified exposure. After alkaline development, it was washed with ultrapure water and then post-baked at 230°C for 20 minutes to form stripe-shaped pixels on the substrate. Subsequently, the chromaticity of the stripe-shaped pixels under a C light source ([L*(1), a*(1), b*(1)]) was measured using a micro-spectrophotometer (Olympus Optical Co., Ltd. "OSP-SP100"). After that, the substrate was immersed in N-methyl-2-pyrrolidone (NMP) or methanol (MeOH) for 15 minutes, and the chromaticity under a C light source after immersion ([L*(2), a*(2), b*(2)]) was measured. The color difference ΔEab* was calculated using the above formula and evaluated using the same criteria as for heat resistance. ΔEab* = √((L*(2)- L*(1))^2+(a*(2)-a*(1)) ^2+(b*(2)-b*(1))^2) ◎: ΔEab* is less than 1.0 (Excellent) ○: ΔEab* is 1.0 or greater, and less than 2.5 (good) △: ΔEab* is 2.5 or greater and less than 5.0 (practical) ×: ΔEab* is 5.0 or higher (not practical)

[0270] <Evaluation of Transmittance> A photosensitive colored composition for color filters was applied to a glass substrate using a slit die coater, and then pre-baked on a 90°C hot plate for 2 minutes. Next, after the substrate with the coated film was cooled to room temperature, radiation containing wavelengths of 365 nm, 405 nm, and 436 nm was applied to the coating film at a rate of 1,000 J / m² using a high-pressure mercury lamp via a striped photomask. 2 The substrate was exposed to light at the specified exposure level. Subsequently, after alkaline development, it was washed with ultrapure water, and then post-baked at 230°C for 20 minutes to form stripe-shaped pixels with a film thickness of 0.5 μm on the substrate. The spectral transmittance of the stripe-shaped pixels at 380-780 nm under a C light source was then measured and evaluated using a micro-spectrophotometer (Olympus Optical Co., Ltd. "OSP-SP100"). ◎: Minimum transmittance of less than 1.0% in the 380-780nm range (extremely good) ○: Minimum transmittance between 380 and 780 nm is 1.0% or higher and less than 2.5% (good). △: Minimum transmittance between 2.5% and 5.0% in the 380-780nm range (practical). ×: Minimum transmittance of 5.0% or higher in the 380-780nm range (not practical)

[0271] [Table 2]

[0272] [Table 3]

[0273] [Table 4]

[0274] [Table 5]

[0275] [Table 6]

[0276] [Table 7] [Explanation of symbols]

[0277] 10 LCD display device 11 Transparent substrate 12 TFT arrays 13 Transparent electrode layer 14. Orientation layer 15 Polarizing plates 21 Transparent substrate 22 Color Filters 23 Transparent electrode layer 24 orientation layer 25 Polarizing plates 30 backlight units 31 White LED light source LC LCD

Claims

1. A photosensitive colored composition comprising a colorant (A), a resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), wherein the content of the colorant (A) is 45 parts by mass or more and 85 parts by mass or less per 100 parts by mass of the total nonvolatile content of the photosensitive colored composition contained in the photosensitive colored composition, and the polymerizable compound (C) comprises a polymerizable compound (C1) having one or more secondary hydroxyl groups and three or more polymerizable unsaturated groups.

2. The photosensitive coloring composition according to claim 1, characterized in that the polymerizable compound (C1) has two or more secondary hydroxyl groups and three polymerizable unsaturated groups.

3. The photosensitive coloring composition according to claim 1, characterized in that the polymerizable compound (C1) has two or more secondary hydroxyl groups and four or more polymerizable unsaturated groups.

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

5. The photosensitive colored composition according to claim 1, characterized in that the resin (B) comprises a dispersion resin (B1), and the dispersion resin (B1) has polymerizable unsaturated groups.

6. A color filter having a filter segment formed by the photosensitive colored composition according to claim 1.

7. A solid-state image sensor comprising the color filter described in claim 6.

8. A liquid crystal display device comprising the color filter described in claim 6.

Images