Photosensitive colored composition, film using the same, color filter, solid-state image sensor, and image display device.

Abstract

To provide a photosensitive coloring composition that can form a cured film with superior adhesion, pattern shape, and surface smoothness, and retains superior developability even after storage.SOLUTION: A photosensitive coloring composition includes a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and a compound (E) represented by the general formula (1). In the general formula (1), R's independently represent an alkyl group, L represents a bivalent linking group, and n represents an integer of 2-10.SELECTED DRAWING: None

Description

[Technical Field]

[0001] This invention relates to a photosensitive coloring composition. [Background technology]

[0002] A color filter is manufactured by, for example, applying a photosensitive colored composition to a transparent substrate such as glass, removing the solvent from the photosensitive colored composition layer (hereinafter referred to as the coating film) by drying (hereinafter referred to as pre-bake), curing the coating film by irradiating it with ultraviolet light or the like through a photomask having a desired pattern (hereinafter referred to as exposure), then cleaning and removing the unexposed parts of the coating film (hereinafter referred to as development), and finally performing a heat treatment (hereinafter referred to as post-bake) to sufficiently harden the cured film to obtain the first color pattern. Then, by performing the same operation, patterns of other colors are formed.

[0003] In recent years, the miniaturization and increased pixel count of image display devices and solid-state image sensors have led to a trend of smaller area per pixel, requiring increased concentration of colorants in photosensitive colored compositions to create thinner films and higher resolution patterns. However, when the colorant concentration is increased, ultraviolet light cannot penetrate deep into the coating film, resulting in poor adhesion such as pattern defects after development due to insufficient photocuring, or peeling of the pattern from the substrate. Furthermore, differences in thermal curing shrinkage between the interior and surface during the subsequent post-bake process can cause wrinkles and other problems on the surface. Increasing the amount of photopolymerization initiator to improve curing also leads to problems such as deterioration of the pattern shape. Moreover, there was a problem where the developability of the photosensitive colored composition changed when stored, such as a slower development time.

[0004] For example, as an effort to improve pattern formation when high concentrations of colorants are included, Patent Document 1 discloses a colored photosensitive resin composition containing a polyfunctional thiol compound and an acetophenone compound. As an effort to improve wrinkles on the surface of the film, Patent Document 2 discloses a colored resin composition containing a photopolymerizable monomer having a double bond equivalent of 400 g / mol or less and having a bisphenol skeleton. Furthermore, Patent Document 3 discloses a photosensitive colored resin composition containing 25% by mass or more of an organic pigment, an alkali-soluble resin, a photopolymerizable compound, and a photopolymerization initiator in the total solids content, wherein the photopolymerization initiator includes an oxime ester-based photopolymerization initiator whose absorbance at a wavelength of 400 nm is 30% or more of the absorbance at the maximum absorption wavelength between 300 and 400 nm, and an oxime ester-based photopolymerization initiator of a specific structure whose absorbance at a wavelength of 400 nm is 10% or less of the absorbance at the maximum absorption wavelength between 300 and 400 nm. [Prior art documents] [Patent Documents]

[0005] [Patent Document 1] Japanese Patent Publication No. 2004-83857 [Patent Document 2] Japanese Patent Publication No. 2019-183053 [Patent Document 3] Japanese Patent Publication No. 2020-148990 [Overview of the project] [Problems that the invention aims to solve]

[0006] However, none of the compositions described in Patent Documents 1 to 3 satisfied all requirements regarding adhesion, pattern shape, surface smoothness, and developability after storage.

[0007] The present invention aims to provide a photosensitive colored composition that can form a cured film with excellent adhesion, pattern shape, and surface smoothness, and that has excellent developability even after storage. [Means for solving the problem]

[0008] The present invention relates to a photosensitive colored composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and a compound (E) represented by the following general formula (1). General formula (1) [ka]

[0009] In general formula (1), each R independently represents an alkyl group. L represents a divalent linking group, and n represents an integer from 2 to 10. [Effects of the Invention]

[0010] According to the present invention described above, it is possible to form a cured film with excellent adhesion, pattern shape, and surface smoothness, and to provide a photosensitive colored composition that has excellent developability even after storage. Furthermore, the present invention can provide a film, a color filter, a solid-state image sensor, and an image display device. [Modes for carrying out the invention]

[0011] The following describes in detail embodiments for carrying out the photosensitive colored composition of the present invention. However, the present invention is not limited to the following embodiments and can be modified and implemented within the scope of solving the problem.

[0012] In this specification, unless otherwise specified, "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" means "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. Also, "CI" means Color Index (CI; issued by The Society of Dyers and Colourists). A polymerizable unsaturated group is an ethylenically unsaturated double bond. Regarding the molecular weight of the compounds in the present invention, for low-molecular compounds whose molecular weight can be specified, it is the value calculated by calculation or the molecular weight measured by ESI-MS (electrospray ionization mass spectrometry). For compounds having a molecular weight distribution, it is the weight-average molecular weight in terms of polystyrene measured by gel permeation chromatography using tetrahydrofuran as a solvent. A monomer is a compound that forms a resin by polymerization. A monomer is in an unreacted state, and a monomer unit is a state in which the monomer forms a resin after polymerization.

[0013] <Photosensitive coloring composition> The photosensitive coloring composition of the present invention is characterized by containing a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and a compound (E) represented by the following general formula (1). General formula (1) [Chemical formula]

[0014] In general formula (1), each R independently represents an alkyl group. L represents a divalent linking group, and n represents an integer of 2 to 10.

[0015] Although the mechanism by which the problems of the present invention can be solved with the photosensitive coloring composition having the above configuration is not clear, it is speculated as follows.

[0016] Since the compound (E) represented by the general formula (1) has six -OR groups (hereinafter referred to as alkoxy groups), the alkoxy groups are liable to hydrolyze and easily react with each other of the compounds (E) represented by the general formula (1), other components contained in the photosensitive coloring composition, the substrate, etc. And a part of (-S-)n (hereinafter referred to as polysulfide bond) cleaves and reacts with the polymerizable unsaturated groups of the alkali - soluble resin (B) and the polymerizable compound (C), whereby a cured film having a sufficient cross - linked structure can be obtained. Therefore, it is presumed that the adhesion is improved, the difference in thermal curing shrinkage between the inside and the surface during post - baking is reduced, and the generation of wrinkles is suppressed. Further, since the sulfide bond and the polysulfide bond are excellent in flexibility, it is presumed that the stress is relaxed and the generation of wrinkles is suppressed. Furthermore, since the polysulfide bond has lower reactivity than the thiol group, it is presumed that it reacts less during the storage of the photosensitive coloring composition, and excellent developability can be obtained even after storage.

[0017] [Colorant (A)] The photosensitive coloring composition of the present invention contains a colorant (A).

[0018] The colorant (A) is not particularly limited and may be either a pigment or a dye, and they can be used in combination. Pigments include organic pigments and inorganic pigments, and for color filter applications, pigments are preferred in terms of light resistance, heat resistance, and solvent resistance.

[0019] (Pigment) The pigment is not particularly limited, and for example, compounds classified as pigments in the Color Index can be mentioned.

[0020] Red pigments include, for example, CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,177,178,179 ,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254,255,256,257,258,259, Examples include pigments 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, pigments described in Japanese Patent Publication No. 2014-134712, pigments described in Japanese Patent Publication No. 6368844, and the like.

[0021] Examples of orange pigments include CI Pigment Orange 36, 38, 43, 64, 71, and 73.

[0022] Yellow pigments include, for example, CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123 Examples include pigments described in JP 2012-226110, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233.

[0023] Furthermore, examples of yellow pigments include pigments containing at least one anion selected from the group consisting of mono, di, tri, and tetraanions of azo compounds represented by the following general formula (2) and tautomerized azo compounds, at least two metal ions selected from Cd, Co, Al, Cr, Sn, Pb, Zn, Fe, Ni, Cu, and Mn, and a compound represented by the following general formula (3).

[0024] General formula (2) [ka]

[0025] In general formula (2), the two R1s each independently represent -OH, -NH2, -NH-CN, an acylamino group, an alkylamino group, or an arylamino group, and the two R2s each independently represent -OH or -NH2.

[0026] General formula (3) [ka]

[0027] In general formula (3), the three R3s each independently represent a hydrogen atom and an alkyl group.

[0028] Examples of green pigments include CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63, etc.

[0029] Examples of blue pigments include CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79, etc.

[0030] Examples of purple pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0031] Examples of black pigments include CI Pigment Black 1, 6, 7, 12, 20, and 31.

[0032] Among these pigments, it is preferable to include at least one selected from the group consisting of CI Pigment Green 7, 36, 58, 59, 62, 63 and CI Pigment Blue 15:2, 15:3, 15:4, 15:6.

[0033] Other examples of inorganic pigments include silica, talc, titanium dioxide, zinc 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, and synthetic iron black.

[0034] It is preferable to use the pigment after it has been finely milled. The milling method is not particularly limited, and for example, wet milling, dry milling, or dissolution milling can all be used. Among these, salt milling by the kneader method, which is a type of wet milling, is preferred. The average primary particle size of the finely milled pigment, as determined by TEM (transmission electron microscopy), is preferably 5 to 90 nm. However, from the viewpoint of dispersibility and contrast ratio, an average primary particle size of 10 to 70 nm is more preferable.

[0035] Resin may be added to the salt milling process as needed. By adding resin, the pigment is coated with resin, improving stability, lightfastness, etc. The type of resin is not particularly limited and includes natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferable that the resin is solid at room temperature, insoluble in water, and partially soluble in organic solvents. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of pigment.

[0036] (dye) Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. In addition, derivatives of these dyes, or lake pigments obtained by lake-forming dyes, can also be used.

[0037] 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.

[0038] 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.

[0039] The chemical structures of dyes include, for example, 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.), azine dyes, and poly Examples of dye structures derived from dyes selected from methine dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, crokonium 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 include, but are not limited to, these.

[0040] 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.

[0041] Coloring agent (A) can be used alone or in combination of two or more types.

[0042] The content of the coloring agent (A) is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0043] [Alkali-soluble resin (B)] The photosensitive colored composition of the present invention contains an alkali-soluble resin (B).

[0044] The alkali-soluble resin (B) is not particularly limited, and any known resin can be used. Examples include (meth)acrylic resin, styrene resin, styrene / (meth)acrylic resin, epoxy resin, urethane resin, polycarbonate resin, polyester resin, polyether resin, polyimide resin, polyamide-imide resin, and cyclic olefin resin.

[0045] The alkali-soluble resin (B) preferably has a weight-average molecular weight (Mw) of 3,000 to 50,000, and more preferably 4,000 to 40,000.

[0046] The acid value of the alkali-soluble resin (B) is preferably 30 to 200 mg KOH / g, and more preferably 40 to 180 mg KOH / g.

[0047] Alkali-soluble resin (B) can be used alone or in combination of two or more types.

[0048] The alkali-soluble resin (B) is preferably present in an amount of 1 to 95% by mass, and more preferably 5 to 80% by mass, of 100% by mass of the non-volatile content of the photosensitive coloring composition.

[0049] (Alkali-soluble resin (B1) having hydroxyl group-containing monomer units (b1)) The alkali-soluble resin (B) preferably contains an alkali-soluble resin (B1) having a hydroxyl group-containing monomer unit (b1) (hereinafter also simply referred to as alkali-soluble resin (B1)) from the viewpoint of adhesion, pattern shape, and surface smoothness. The reaction between the hydroxyl groups in the alkali-soluble resin (B1) and the compound (E) represented by general formula (1) improves adhesion, pattern shape, and surface smoothness.

[0050] The alkali-soluble resin (B1) having a hydroxyl group-containing monomer unit (b1) is not particularly limited as long as it is an alkali-soluble resin having a hydroxyl group, and can be produced by known methods. For example, it can be produced by the methods (i) to (iii) shown below.

[0051] <Method (i)> There is a method (i) for copolymerizing a hydroxyl group-containing monomer that forms a hydroxyl group-containing monomer unit (b1) and a monomer that can be arbitrarily copolymerized with it.

[0052] [Hydroxyl group-containing monomer unit (b1)] Examples of hydroxyl group-containing monomers include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and 2-acryloyloxyethyl-2-hydroxyethyl phthalic acid.

[0053] The copolymerizable monomers are not particularly limited, and known compounds can be used. Examples include the acidic group-containing monomers, epoxy group-containing monomers, alicyclic hydrocarbon-containing monomers, aromatic ring-containing monomers, isocyanate group-containing monomers (the isocyanate group may be protected with a blocking agent), and other monomers, as described later.

[0054] <Method (ii)> (ii) One method involves introducing hydroxyl groups by adding a compound containing carboxyl groups (modified compound) to the epoxy groups contained in the resin (precursor).

[0055] <Method (iii)> (iii) One method involves introducing hydroxyl groups by adding a compound containing epoxy groups (modified compound) to the carboxyl groups contained in the resin (precursor).

[0056] From the viewpoint of adhesion, pattern shape, surface smoothness, and developability after storage, the content of hydroxyl group-containing monomer units (b1) is preferably 1 to 60 mol%, and more preferably 5 to 40 mol%, of the total constituent units of the alkali-soluble resin (B1).

[0057] The alkali-soluble resin (B1) may contain, in addition to hydroxyl group-containing monomer units (b1), acid group-containing monomer units (b2), epoxy group-containing monomer units (b3), alicyclic hydrocarbon-containing monomer units (b4), aromatic ring-containing monomer units (b5), isocyanate group-containing monomer units (b6), polymerizable unsaturated group-containing monomer units (b7), and other monomer units (b8).

[0058] [Acidic group-containing monomer unit (b2)] From the viewpoint of pattern shape and developability, the alkali-soluble resin (B1) preferably has an acidic group-containing monomer unit (b2). Examples of acidic group-containing monomers include (meth)acrylic acid, crotonic acid, propiolic acid, cinnamic acid, itaconic acid, itaconic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, monoisopropyl maleate, maleic anhydride, fumaric acid, 2-methacryloyloxyethyl succinic acid, 2-acryloyloxyethyl phthalic acid, 2-acryloyloxyethylhexyl hydrophthalic acid, p-styrene sulfonic acid, vinyl sulfonic acid, 2-acrylamido-2-methylpropanesulfonic acid, tert-butylacrylamidosulfonic acid, and 2-(meth)acryloyloxyethyl acid phosphate.

[0059] [Epoxy group-containing monomer unit (b3)] The alkali-soluble resin (B1) may have epoxy group-containing monomer units (b3). Examples of epoxy group-containing monomers include oxyranyl (meth)acrylate, glycidyl (meth)acrylate, 2-methylglycidyl (meth)acrylate, 2-ethylglycidyl (meth)acrylate, 2-oxyranyl ethyl (meth)acrylate, 2-glycidyloxyethyl (meth)acrylate, 3,4-epoxycyclohexyl (meth)acrylate, 3,4-epoxycyclohexylmethyl (meth)acrylate, 2-(3,4-epoxycyclohexyl)ethyl (meth)acrylate, 2-(3,4-epoxycyclohexylmethyloxy)ethyl (meth)acrylate, and 3-(3,4-epoxycyclohexylmethyloxy)propyl (meth)acrylate.

[0060] [Alicyclic hydrocarbon-containing monomer units (b4)] From the viewpoint of adhesion and pattern shape, the alkali-soluble resin (B1) preferably has alicyclic hydrocarbon-containing monomer units (b4). Examples of alicyclic hydrocarbon-containing monomers include isobolonyl (meth)acrylate, cyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentanyloxyethyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, and adamantyl (meth)acrylate. Among these, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and dicyclopentanyloxyethyl (meth)acrylate are preferred.

[0061] [Aromatic ring-containing monomer unit (b5)] From the viewpoint of adhesion and pattern shape, the alkali-soluble resin (B1) preferably has aromatic ring-containing monomer units (b5). Examples of aromatic ring-containing monomers include styrene, α-methylstyrene, vinylnaphthalene, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, paracumylphenol ethylene oxide (EO) or propylene oxide (PO) modified (meth)acrylate, phenol EO or PO modified (meth)acrylate, nonylphenol EO or PO modified (meth)acrylate, N-phenylmaleimide, and N-benzylmaleimide. Among these, styrene, benzyl (meth)acrylate, paracumylphenol ethylene oxide (EO) or propylene oxide (PO) modified (meth)acrylate are preferred.

[0062] [Isocyanate group-containing monomer unit (b6)] The alkali-soluble resin (B1) may have isocyanate group-containing monomer units (b6). From the viewpoint of developability after storage, it is preferable to protect the isocyanate group-containing monomer units (b6) with a heat-release compound (blocking agent).

[0063] Examples of isocyanate group-containing monomers include 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate. Equimolar reaction products of 2-hydroxyalkyl (meth)acrylate and diisocyanate compounds can also be used.

[0064] Examples of blocking agents include oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, imide compounds, urea compounds, imine compounds, and bisulfite compounds.

[0065] Examples of oxime compounds include formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, and benzophenone oxime. Among these, methyl ethyl ketoxime is preferred. Examples of lactam compounds include ε-caprolactam, δ-valerolactam, γ-butyrolactam, and β-propiolactam. Examples of phenolic compounds include phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, p-tert-butylphenol, nonylphenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, p-naphthol, and p-nitrophenol. Among these, 3,5-xylenol, methyl 2-hydroxybenzoate, and methyl 4-hydroxybenzoate are preferred. Examples of alcohol compounds include methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, and furfuryl alcohol. Examples of amine compounds include diphenylamine, phenylnaphthylamine, aniline, and carbazole. Examples of active methylene compounds include dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, and acetylacetone, with diethyl malonate being preferred. Examples of pyrazole compounds include pyrazole, methylpyrazole, and 3,5-dimethylpyrazole, with 3,5-dimethylpyrazole being preferred. Examples of mercaptan compounds include butyl mercaptan, thiophenol, and tert-dodecyl mercaptan. Examples of imidazole compounds include imidazole, 2-methylimidazole, 2-ethylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, and 1-benzyl-2-phenylimidazole. Examples of imide compounds include succinimide, maleimide, maleimide, and phthalimide. Examples of urea compounds include urea, thiourea, and ethyleneurea. Examples of imine compounds include ethyleneimine and polyethyleneimine. Examples of bisulfite compounds include sodium bisulfite and potassium bisulfite.

[0066] Blocking agents can be used alone or in combination of two or more types.

[0067] The blocking agent is preferably one or more selected from the group consisting of oxime compounds, lactam compounds, phenol compounds, alcohol compounds, amine compounds, active methylene compounds, pyrazole compounds, mercaptan compounds, imidazole compounds, and imide compounds, and more preferably one or more selected from the group consisting of oxime compounds, phenol compounds, active methylene compounds, and pyrazole compounds from the viewpoint of protective and deprotective reactions.

[0068] Examples of monomers containing blocked isocyanate groups include the following compounds. However, the present invention is not limited to these.

[0069] [ka]

[0070] Examples of commercially available monomers containing blocked isocyanate groups include Karens MOI-DEM (blocking agent desorption temperature: 85-95°C), MOI-BP (blocking agent desorption temperature: 105-115°C), and MOI-BM (blocking agent desorption temperature: 125-135°C), all manufactured by Showa Denko Corporation.

[0071] [Polymerizable unsaturated group-containing monomer unit (b7)] From the viewpoint of adhesion, pattern shape, and surface smoothness, the alkali-soluble resin (B1) preferably has polymerizable unsaturated group-containing monomer units (b7). There are no particular restrictions on the method for introducing polymerizable unsaturated group-containing monomer units (b7), and known methods can be used. For example, the methods (iv) to (vi) shown below are available.

[0072] <Method (iv)> (iv) One method involves adding the acidic group of the aforementioned acidic group-containing monomer (modified compound) to the epoxy group contained in the resin (precursor).

[0073] <Method(v)> (v) One method involves adding the epoxy group of the epoxy group-containing monomer (modified compound) described above to the acidic group contained in the resin (precursor).

[0074] Furthermore, the hydroxyl groups produced by the reactions in methods (iv) and (v) can be further reacted with an acid anhydride (modified compound) to introduce acidic groups.

[0075] Examples of acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, and maleic anhydride.

[0076] <Method (vi)> (vi) One method involves reacting the hydroxyl groups contained in the resin (precursor) with the isocyanate groups of the isocyanate group-containing monomer (modified compound) mentioned above.

[0077] [Other monomer units (b8)] The alkali-soluble resin (B1) may have other monomer units (b8). Other monomers include acrylic acid esters such as ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, tert-butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, lauryl (meth)acrylate, dimethylaminoethyl (meth)acrylate, and diethylaminoethyl (meth)acrylate; (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, or acryloylmorpholine; Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; Vinyl acetate or vinyl propionate, and other fatty acid vinyl compounds; N-substituted maleimides such as methyl maleimide, ethyl maleimide, 1,2-bismaleimideethane, 1,6-bismaleimidehexane, 3-maleimidepropionic acid, and 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin; Examples include dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-propenoate, and di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-propenoate.

[0078] The weight-average molecular weight (Mw) of the alkali-soluble resin (B1) is preferably 3,000 to 50,000, and more preferably 4,000 to 40,000.

[0079] The acid value of the alkali-soluble resin (B1) is preferably 30 to 200 mg KOH / g, and more preferably 40 to 180 mg KOH / g.

[0080] Alkali-soluble resin (B1) can be used alone or in combination of two or more types.

[0081] The content of alkali-soluble resin (B1) is preferably 10 to 100% by mass, and more preferably 20 to 100% by mass, of alkali-soluble resin (B) by mass.

[0082] [Polymerizable compound (C)] The photosensitive coloring composition of the present invention contains a polymerizable compound (C).

[0083] Polymerizable compounds (C) include monomers and oligomers having polymerizable unsaturated groups. Examples of polymerizable unsaturated groups include vinyl groups, (meth)allyl groups, (meth)acryloyl groups, and (meth)acryloyloxy groups. Examples of polymerizable compounds (C) include polymerizable compounds having hydroxyl groups (C1), polymerizable compounds having acidic groups (C2), polymerizable compounds having urethane bonds (C3), lactone-modified polymerizable compounds (C4), polymerizable compounds having a tertiary amine structure (C5), polymerizable compounds having a dendrimer structure or hyperbranch structure (C6), and other polymerizable compounds (C7).

[0084] (Molybdenum-containing polymerizable compound (C1)) The photosensitive colored composition of the present invention preferably contains a polymerizable compound (C1) having a hydroxyl group as the polymerizable compound (C) from the viewpoint of adhesion, pattern shape, and surface smoothness. The hydroxyl group in the polymerizable compound (C1) having a hydroxyl group reacts with the compound (E) represented by general formula (1), thereby improving adhesion, pattern shape, and surface smoothness.

[0085] Polymerizable compounds (C1) having a hydroxyl group include, for example, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, 2,3-hydroxypropyl (meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, cyclohexanedimethanol mono(meth)acrylate, 2-hydroxy-3-phenoxypropyl acrylate, and Examples include acrylic acid esters such as sorbic acid EO or PO-modified (meth)acrylate, isocyanuric acid EO or PO-modified di(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, polypentaerythritol penta(meth)acrylate, dipentaerythritol EO or PO-modified penta(meth)acrylate, and dipentaerythritol caprolactone-modified penta(meth)acrylate, as well as epoxy(meth)acrylates obtained by reacting the epoxy group of an epoxy compound with the carboxyl group of (meth)acrylic acid. Among these, pentaerythritol tri(meth)acrylate and dipentaerythritol penta(meth)acrylate are preferred.

[0086] Examples of commercially available polymerizable compounds (C1) containing hydroxyl groups include KAYARAD R-128H and R-167 from Nippon Kayaku Co., Ltd., Aronix M-5700, M-920, and M-930 from Toagosei Co., Ltd., NK Ester 701A from Shin Nakamura Chemical Co., Ltd., Light Ester HOP(N), HOA(N), HOP-A(N), HOB(N), and G-201P from Kyoeisha Chemical Co., Ltd., and epoxy esters M-600A, 40EM, 70PA, 200PA, 80MFA, 3002M(N), 3002A(N), and 3000A from Osaka Gas Chemical Co., Ltd., and OGSOL GA-5060P and GA-2800 from Osaka Gas Chemical Co., Ltd.

[0087] The content of the polymerizable compound (C1) having a hydroxyl group is preferably 10 to 80% by mass, and more preferably 20 to 70% by mass, based on 100% by mass of polymerizable compound (C).

[0088] (Polymerizable compound (C2) containing an acidic group) Examples of polymerizable compounds (C2) having an acidic group include esters of polyhydric alcohols and (meth)acrylic acid-containing poly(meth)acrylates with free hydroxyl groups and dicarboxylic acids; and esters of polyhydric acids and monohydroxyalkyl (meth)acrylates. Note that polymerizable compounds (C2) having an acidic group are compounds that do not contain urethane bonds.

[0089] Examples of the polyhydric alcohols mentioned above include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, and dipentaerythritol.

[0090] Examples of the dicarboxylic acids mentioned above include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, and itaconic acid.

[0091] Examples of the polycarboxylic acids mentioned above include trimellitic acid and pyromellitic acid. Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, pentaerythritol triacrylate, and 2-hydroxy-3-acryloyloxypropyl methacrylate.

[0092] Examples of commercially available polymerizable compounds (C2) containing acidic groups include Viscoat #2500P from Osaka Organic Chemical Industry Co., Ltd., Aronics M-5300, M-5400, M-510, M-520, and M-521 from Toagosei Co., Ltd., and β-CEA from Daicel Ornex Co., Ltd.

[0093] (Polymerizable compound (C3) containing urethane bonds) From the viewpoint of surface smoothness, the photosensitive colored composition of the present invention is particularly preferably composed of a polymerizable compound (C3) having a urethane bond as the polymerizable compound (C). The physical crosslinking structure due to intermolecular hydrogen bonding of the urethane bond has appropriate flexibility, thereby relieving stress and suppressing the occurrence of wrinkles.

[0094] Polymerizable compounds (C3) having a urethane bond include, for example, urethane (meth)acrylates obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and then reacting it with a hydroxyl group-containing (meth)acrylate.

[0095] Examples of the hydroxyl group-containing (meth)acrylates mentioned above 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 (EO)-modified penta(meth)acrylate, dipentaerythritol propylene oxide (PO)-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol mono(meth)acrylate, glycerol di(meth)acrylate, glycerol tri(meth)acrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction products of epoxy group-containing compounds and carboxy(meth)acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

[0096] Examples of the polyfunctional isocyanates mentioned above include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate; aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; and alicyclic diisocyanates such as isophorone diisocyanate, as well as their bilets, isocyanate nulates, and trimethylolpropane adducts.

[0097] From the viewpoint of pattern shape and surface smoothness, the number of polymerizable unsaturated groups in the polymerizable compound (C3) having urethane bonds is preferably 5 to 12.

[0098] The molecular weight of the polymerizable compound (C3) having a urethane bond is preferably 500 to 5,000, more preferably 500 to 3,000, and particularly preferably 500 to 2,000, from the viewpoint of pattern shape and surface smoothness.

[0099] Polymerizable compounds (C3) having urethane bonds are preferably further endowed with acidic groups from the viewpoint of developability and pattern shape. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphate groups. Among these, carboxyl groups are preferred.

[0100] One method for introducing an acidic group into a polymerizable compound (C3) having a urethane bond is to first react the hydroxyl group-containing (meth)acrylate with the polyfunctional isocyanate, and then add a mercapto compound having a carboxyl group to the product.

[0101] Examples of mercapto compounds having the carboxyl group mentioned above include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0102] Examples of commercially available polymerizable compounds (C3) containing urethane bonds include AH-600, UA-306H, UA-306T, UA-306I, UA-510H, and UF-8001G from Kyoeisha Chemical Co., Ltd., UA-1100H, U-6LPA, UA-33H, U-10HA, and U-15HA from Shin Nakamura Chemical Co., Ltd., and EBECRYL1290 and KRM8452 from Daicel Ornex Co., Ltd.

[0103] The content of polymerizable compound (C3) having a urethane bond is preferably 10 to 80% by mass, and more preferably 20 to 70% by mass, based on 100% by mass of polymerizable compound (C).

[0104] (Lactone-modified polymerizable compound (C4)) Lactone-modified polymerizable compounds (C4) are compounds that have a structure modified with lactone within their molecule. Lactone-modified polymerizable compounds (C4) are obtained by esterifying polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethythritol, tripentaerythritol, glycerin, diglycerol, and trimetrolmelamine with (meth)acrylic acid and ε-caprolactone or other lactone compounds.

[0105] Examples of commercially available lactone-modified polymerizable compounds (C4) include KAYARAD DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd.

[0106] (A polymerizable compound (C5) having a tertiary amine structure) Polymerizable compounds (C5) having a tertiary amine structure include, for example, tris(acryloyloxyethyl)amine, tris(methacryloyloxyethyl)amine, tris(2-hydroxy-3-methacryloyloxypropyl)amine, and Michael addition reaction products of (meth)acrylate compounds (X) and amine compounds (Y).

[0107] (Meth)acrylate compound (X) is, for example, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, diglycerin Examples include lint tri(meth)acrylate, diglycerin tetra(meth)acrylate, trimethylolpropane alkylene oxide-modified tri(meth)acrylate, ditrimethylolpropane alkylene oxide-modified tri and tetra(meth)acrylate, pentaerythritol alkylene oxide-modified tri and tetra(meth)acrylate, diglycerin alkylene oxide-modified tri and tetra(meth)acrylate, and dipenerythritol alkylene oxide-modified tetra, penta, and hexa(meth)acrylate. Examples of alkylene oxide units in the alkylene oxide modification include ethylene oxide, propylene oxide, and butylene oxide. Furthermore, (meth)acrylate compounds (X) can also include (meth)acrylate compounds having an acidic group.

[0108] (Meth)acrylate compound (X) can be used alone or in combination of two or more types.

[0109] Amine compound (Y) is a primary amine such as n-propylamine, n-butylamine, n-hexylamine, benzylamine, aminocaproic acid, monoethanolamine, 2-(2-aminoethoxy)ethanol, o-aminophenol, m-aminophenol, p-aminophenol, etc. Examples include dimethylamine, diethylamine, dipropylamine, diisopropylamine, dibutylamine, cyclohexylamine, morpholine, piperidine, 1-methylpiperazine, proline, N-merylethanolamine, N-acetylethanolamine, diethanolamine, 3-anilynphenol, 4-anilynphenol, and other secondary amines.

[0110] Amine compound (Y) can be used alone or in combination of two or more types.

[0111] There are no particular limitations on the method for producing the Michael addition reaction product of a (meth)acrylate compound (X) and an amine compound (Y), and known methods can be used. For example, the methods described in International Publication No. 2006 / 075754, Japanese Patent Publication No. 2008-545859, and Japanese Patent Application Publication No. 2017-066347 are examples.

[0112] A polymerizable compound (C5) having a tertiary amine structure may have an acidic group and / or a hydroxyl group. Methods for introducing an acidic group and / or a hydroxyl group include, for example, using a compound having an acidic group and / or a hydroxyl group with a (meth)acrylate compound (X) or an amine compound (Y), or adding an acid anhydride after a Michael addition reaction.

[0113] Examples of commercially available polymerizable compounds (C5) having a tertiary amine structure include Aronics MT-3041 and MT-3042 manufactured by Toagosei Co., Ltd.

[0114] (Polymerizable compounds (C6) having a dendrimer structure or hyperbranch structure) Polymerizable compounds having a dendrimer structure have a chemical structure in which a core (hereinafter also referred to as the core portion) repeatedly branches outwards in a regular manner, with polymerizable unsaturated groups bonded to the ends of these branches. They have a highly controlled spherical chemical structure and molecular weight. Hyperbranched structures have a chemical structure similar to that of dendrimer structures.

[0115] Examples of commercially available polymerizable compounds (C6) having a dendrimer or hyperbranched structure include Viscoat #1000LT (dendrimer structure, average acryloyl group count 14) from Osaka Organic Chemical Industry Co., Ltd., Miramer SP-1106 (dendrimer structure, average acryloyl group count 18), SP-1108 (dendrimer structure, average acryloyl group count 13) from Miwon Specialty Chemical Co., Ltd., CN2301 (hyperbranched structure, average acryloyl group count 9), CN2302 (hyperbranched structure, average acryloyl group count 16), CN2303 (hyperbranched structure, average acryloyl group count 6), CN2304 (hyperbranched structure, average acryloyl group count 18) from SARTOMER, and Eternal Examples include Etercure 6361-100 (hyperbranch structure, average acryloyl group count 8), 6362-100 (hyperbranch structure, average acryloyl group count 12), 6363 (hyperbranch structure, average acryloyl group count 16), and DR-E522 (hyperbranch structure, average acryloyl group count 15), all manufactured by Materials Inc.

[0116] (Other polymerizable compounds (C7)) Other polymerizable compounds (C7) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (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 EO or PO-modified tri(meth)acrylate, isocyanuric acid EO or PO-modified tri(meth)acrylate Examples include ditrimethylolpropanetetra(meth)acrylate, pentaerythritoltetra(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol EO or PO-modified hexa(meth)acrylate, dipentaerythritol caprolactone-modified hexa(meth)acrylate, tricyclodecanyl(meth)acrylate, (meth)acrylic acid esters such as (meth)acrylic acid esters of methylolated melamine, styrene, vinyl acetate, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0117] Other commercially available polymerizable compounds (C7) include, for example, KAYARAD NPGDA, PEG400DA, FM-400, HX-200, HX-620, R-551, R-712, R-604, R-684, GPOD-303, TMPTA, T-1420(T), RP-1040, DPEA-12, D-310 from Nippon Kayaku Co., Ltd., and Aronix M-101A, M-102, M-111, M-113, M-120, M-140, M-208, M-21 from Toagosei Co., Ltd. 1B, M-220, M-225, M-270, M-240, M-309, M-310, M-321, M-350, M-360, M-408, M-460; Viscoat #150, #155, #160, #192, #MTG, #200, #196, #195, #230, #260, #310, #700HV, #295 from Osaka Organic Chemical Industry Co., Ltd.; OGSOL from Osaka Gas Chemical Co., Ltd. Examples include EA-0200, EA-0300, Miramer HR6060, 6100, 6200 from Miwon Specialty Chemical Co., Ltd., and NK esters A-HD-N, A-NPG, A-200, A-400, APG-200, APG-400, A-DCP, ABE-300, A-BPE-4, A-BPE-10, A-TMPT, A-TMPT-9EO, A-GLY-3E, A-GLY-9E, A-TMMT, ATM-35E, AD-TMP from Shin Nakamura Chemical Industry Co., Ltd.

[0118] Polymerizable compound (C) can be used alone or in combination of two or more types.

[0119] The content of polymerizable compound (C) is preferably 5 to 70% by mass, and more preferably 10 to 60% by mass, based on 100% by mass of the nonvolatile content of the photosensitive colored composition.

[0120] [Polymerization initiator (D)] The photosensitive colored composition of the present invention contains a polymerization initiator (D).

[0121] The polymerization initiator (D) is not particularly limited, and known compounds can be used. For example, compounds that generate radicals by the action of light or heat to initiate or accelerate the radical polymerization reaction can be used. A polymerization initiator that generates radicals in response to light (hereinafter also simply referred to as a photopolymerization initiator) is preferably a compound that generates radicals in response to light from ultraviolet to visible light. A polymerization initiator that generates radicals by heat (hereinafter also simply referred to as a thermal polymerization initiator) may be a compound that generates radicals by the action of heat and light.

[0122] Examples of photopolymerization initiators include acetophenone compounds such as 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-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; Triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-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-methoxy-naphtho-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; Oxime compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyl oxime)], or etanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole3-yl]-,1-(O-acetyl oxime); Acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; and carbazole compounds.

[0123] Commercially available products include: acetophenone compounds such as Omnirad907, 369E, 379EG, 127, 184, 1173, and 2959 from IGM Resins; acylphosphine compounds such as Omnirad819 and TPO from IGM Resins; oxime compounds such as IRGACURE OXE-01, 02, 03, and 04 from BASF Japan; ADEKA's ADEKA Arclus N-1919T, NCI-730, NCI-831E, and NCI-930 from ADEKA; and TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, and 3057 from Changzhou Strong New Materials Co., Ltd. Examples include Omnirad 1312, 1314, and 1316 from Resins, SPI-02, 03, 04, 05, 06, and 07 from Samyang Corporation, and DFI-020, 306, and EOX-01 from Daito Chemix. Also, compounds described in Japanese Patent Publication No. 2007-210991, 2009-179619, 2010-037223, 2010-215575, 2011-020998, International Publication No. 2015 / 036910, Japanese Patent Publication No. 2019-507108, Japanese Patent Publication No. 2019-528331, and International Publication No. 2021 / 175855 are also examples. Among these, oxime compounds are preferred from the viewpoint of adhesion, pattern shape, and surface smoothness.

[0124] The following are specific examples of oxime compounds. However, the present invention is not limited to these.

[0125] [ka]

[0126] Among these, the oxime compounds (D-1) to (D-4) are preferred.

[0127] Examples of thermal polymerization initiators include benzopinacol, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetraphenylethane, 1,2-diphenoxy-1,1,2,2-tetraphenylethane, 1,2-dimethoxy-1,1,2,2-tetra(4-methylphenyl)ethane, 1,2-diphenoxy-1,1,2,2-tetra(4-methoxyphenyl)ethane, and 1,2-bis(trimethylsiloxy)-1,1,2,2-tetraphenylethane. Pinacol compounds such as 1,2-bis(triethylsiloxy)-1,1,2,2-tetraphenylethane, 1,2-bis(tert-butyldimethylsiloxy)-1,1,2,2-tetraphenylethane, 1-hydroxy-2-trimethylsiloxy-1,1,2,2-tetraphenylethane, 1-hydroxy-2-triethylsiloxy-1,1,2,2-tetraphenylethane, and 1-hydroxy-2-tert-butyldimethylsiloxy-1,1,2,2-tetraphenylethane; Azo compounds such as 2,2'-azobis(4-methoxy-2,4-dimethylvaleronitrile), 2,2'-azobis(2,4-dimethylvaleronitrile), dimethyl-2,2'-azobis(2-methylpropionate), 2,2'-azobis(2-methylbutyronitrile), 1,1'-azobis(cyclohexane-1-carbonnitrile), 2,2'-azobis[N-(2-propenyl)2-methylpropionamide], 1-[(1-cyano-1-methylethyl)azo]formamide, 2,2'-azobis(N-butyl-2-methylpropionamide), and 2,2'-azobis(N-cyclohexyl-2-methylpropionamide); Examples include organic peroxides such as methyl ethyl ketone peroxide, cyclohexanone peroxide, 3,3,5-trimethylcyclohexanone peroxide, methylcyclohexanone peroxide, acetylacetone peroxide, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, 1,1-bis(tert-butylperoxy)cyclohexane, 2,2-bis(tert-butylperoxy)butane, succinic acid peroxide, and benzoyl peroxide. Among these, pinacol compounds are preferred.

[0128] Polymerization initiator (D) can be used alone or in combination of two or more types.

[0129] The content of polymerization initiator (D) is preferably 0.1 to 20% by mass, and more preferably 0.5 to 10% by mass, based on 100% by mass of the nonvolatile content of the photosensitive colored composition.

[0130] (Compound (E) represented by general formula (1)) The photosensitive colored composition of the present invention contains compound (E) represented by the following general formula (1).

[0131] General formula (1) [ka]

[0132] In general formula (1), each R independently represents an alkyl group. L represents a divalent linking group, and n represents an integer from 2 to 10.

[0133] In general formula (1), each R independently represents an alkyl group. The alkyl group may be linear or branched, and is preferably a substituted or unsubstituted alkyl group having 1 to 10 carbon atoms, and more preferably an unsubstituted alkyl group having 1 to 6 carbon atoms. Among these, a methyl group or an ethyl group is preferred from the viewpoint of pattern shape and surface smoothness, and an ethyl group is more preferred from the viewpoint of developability after storage.

[0134] In general formula (1), L represents a divalent linking group. Examples of divalent linking groups include alkylene groups, arylene groups, or combinations thereof. Alkylene groups may be linear or branched, and substituted or unsubstituted alkylene groups having 1 to 10 carbon atoms are preferred. Arylene groups having 6 to 12 carbon atoms, substituted or unsubstituted, are preferred.

[0135] In general formula (1), n ​​represents an integer from 2 to 10. From the viewpoint of adhesion, pattern shape, surface smoothness, and developability after storage, n is preferably from 2 to 6, and more preferably from 2 to 4.

[0136] There are no particular limitations on the method for producing compound (E) represented by general formula (1), and known methods can be used. For example, the methods described in Japanese Patent Publication No. 8-198883, Japanese Patent Publication No. 10-175981, Japanese Patent Publication No. 11-100388, etc.

[0137] The following are specific examples of compound (E) represented by general formula (1). However, the present invention is not limited to these examples.

[0138] [ka]

[0139] The content of compound (E) represented by general formula (1) is preferably 0.5 to 15 parts by mass, and more preferably 1.5 to 12 parts by mass, per 100 parts by mass of the total of alkali-soluble resin (B) and polymerizable compound (C), from the viewpoint of adhesion, pattern shape, surface smoothness, and developability after storage.

[0140] From the viewpoint of adhesion, pattern shape, and surface smoothness, it is preferable to use at least two compounds (E) represented by general formula (1).

[0141] The compound (E) represented by general formula (1) preferably contains a compound with n=2, from the viewpoint of adhesion, pattern shape, and surface smoothness.

[0142] The content of the compound n=2 is preferably 30% by mass or more, and more preferably 40-95% by mass, of 100% by mass of compound (E) represented by general formula (1), from the viewpoint of adhesion, pattern shape, and surface smoothness.

[0143] [Dye derivative (F)] The photosensitive colored composition of the present invention may contain a dye derivative (F).

[0144] The dye derivative (F) is not particularly limited and can include dye derivatives having acidic groups, basic groups, neutral groups, etc., in the organic dye residue. Examples of dye derivatives (F) include compounds having acidic substituents such as sulfo groups, carboxyl groups, and phosphate groups, as well as amine salts thereof, compounds having basic substituents such as sulfonamide groups or tertiary amino groups at the terminal, and compounds having neutral substituents such as phenyl groups or phthalimidoalkyl groups. Examples of organic pigments 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, and azo pigments such as azo, disazo, and polyazo.

[0145] Specifically, diketopyrrolopyrrole dye derivatives include JP 2001-220520, International Publication No. 2009 / 081930, International Publication No. 2011 / 052617, International Publication No. 2012 / 102399, and JP 2017-156397; phthalocyanine dye derivatives include JP 2007-226161, International Publication No. 2016 / 163351, JP 2017-165820, and Patent No. 5753266; and anthraquinone dye derivatives include JP Sho 63-264 Japanese Patent Publication No. 674, Japanese Patent Publication No. 09-272812, Japanese Patent Publication No. 10-245501, Japanese Patent Publication No. 10-265697, Japanese Patent Publication No. 2007-079094, International Publication No. 2009 / 025325, as quinacridone-based dye derivatives, Japanese Patent Publication No. 48-54128, Japanese Patent Publication No. 03-9961, Japanese Patent Publication No. 2000-273383, as dioxazine-based dye derivatives, Japanese Patent Publication No. 2011-162662, as thiaidine-indigo-based dye derivatives, Japanese Patent Publication No. 2007-314785, triazine Examples of benzoindole-based dye derivatives include Japanese Patent Publication No. 61-246261, Japanese Patent Publication No. 11-199796, Japanese Patent Publication No. 2003-165922, Japanese Patent Publication No. 2003-168208, Japanese Patent Publication No. 2004-217842, and Japanese Patent Publication No. 2007-314681. Examples of benzoisoindole-based dye derivatives include Japanese Patent Publication No. 2009-57478. Examples of quinophthalone-based dye derivatives include Japanese Patent Publication No. 2003-167112, Japanese Patent Publication No. 2006-291194, Japanese Patent Publication No. 2008-31281, and Japanese Patent Publication No. 2012-226 Examples of known dye derivatives include those described in Japanese Patent Publication No. 110, Japanese Patent Publication No. 2012-208329 and Japanese Patent Publication No. 2014-5439 as naphthol-based dye derivatives, Japanese Patent Publication No. 2001-172520 and Japanese Patent Publication No. 2012-172092 as azo-based dye derivatives, Japanese Patent Publication No. 2004-307854 as an acidic substituent, and Japanese Patent Publication No. 2002-201377, Japanese Patent Publication No. 2003-171594, Japanese Patent Publication No. 2005-181383 and Japanese Patent Publication No. 2005-213404 as basic substituents.In addition, these documents may refer to dye derivatives as derivatives, pigment derivatives, dispersants, pigment dispersants, or simply compounds, but compounds having substituents such as acidic groups, basic groups, or neutral groups on the aforementioned organic dye residues are synonymous with dye derivatives.

[0146] The dye derivative (F) can be used alone or in combination of two or more types.

[0147] The content of the pigment derivative (F) is preferably 1 to 20 parts by mass, and more preferably 2 to 10 parts by mass, per 100 parts by mass of the coloring agent (A).

[0148] [Dispersion resin (G)] The photosensitive colored composition of the present invention may contain a dispersion resin (G).

[0149] The dispersion resin (G) is not particularly limited as long as it is a resin with dispersive properties, and known resins can be used. In particular, it is preferable that it has an adsorption group that has a high affinity for the colorant (A), and it is more preferable that the adsorption group has one or more basic groups and acidic groups.

[0150] Basic groups include, for example, primary amino groups, secondary amino groups, tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocycles and other groups containing nitrogen atoms.

[0151] Examples of acidic groups include carboxyl groups, phosphate groups, and sulfonic acid groups. Among these, carboxyl groups and phosphate groups are preferred from the viewpoint of adsorption to pigments and developability.

[0152] Examples of the resin types of the dispersed resin (G) 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.

[0153] Examples of the structure of the dispersion resin (G) include random structures, block structures, graft structures, comb structures, and star structures. Among these, block structures, graft structures, and comb structures are preferred from the viewpoint of dispersion stability.

[0154] Commercially available dispersion resins (G) include, for example, Disperbyk-101, 103, 107, 108, 110, 111, 116, 130, 140, 154, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 21 SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 325, etc. manufactured by Lubrizol Japan, including 64, or Anti-Terra-U203, 204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen. 50, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500 etc., BASF Japan EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 45 Examples of resins include 1,453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., Ajisuper PA111, PB711, PB821, PB822, PB824 etc. manufactured by Ajinomoto Fine Techno Co., Ltd., and resins described in Japanese Patent Publication No. 2008-029901, Japanese Patent Publication No. 2009-155406, Japanese Patent Publication No. 2010-185934, Japanese Patent Publication No. 2011-157416, etc.

[0155] The dispersion resin (G) can be used alone or in combination of two or more types.

[0156] The content of the dispersion resin (G) is preferably 3 to 200 parts by mass, and more preferably 5 to 100 parts by mass, per 100 parts by mass of the coloring agent (A).

[0157] [Sensitizer (H)] The photosensitive colored composition of the present invention may contain a sensitizer (H).

[0158] The sensitizer (H) is, for example, a polymethine dye such as chalcone derivatives, unsaturated ketones represented by dibenzalacetone, 1,2-diketone derivatives represented by 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, 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, tetrapyrazinoporphyra Examples include din derivatives, 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, organoruthenium complexes, or Michler ketone derivatives, α-acyloxyesters, acyl oxides, methylphenylglyoxylates, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, and the like.

[0159] Among the sensitizers (H), thioxanthone derivatives, Michler ketone derivatives, and carbazole derivatives are preferred. Specific compounds that are preferred include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole.

[0160] Sensitizer (H) can be used alone or in combination of two or more types.

[0161] The content of the sensitizer (H) is preferably 3 to 60 parts by mass, and more preferably 5 to 50 parts by mass, per 100 parts by mass of the polymerization initiator (D).

[0162] [Thermosetting compound (I)] The photosensitive colored composition of the present invention may contain a thermosetting compound (I).

[0163] Thermosetting compound (I) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of thermosetting compound (I) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0164] (Epoxy compound) 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, vinylnolbornene, tetrahydroindene, divinylbenzene, etc.). Examples include polymers of divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc., polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), 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 obtained by glycidylating alcohols, etc.

[0165] Commercially available epoxy compounds include, for example, Epicote 807, 815, 825, 827, 828, 190P, and 191P from Shell Epoxy Corporation, and TECHMORE from Mitsui Chemicals. VG3101L, EPPN-201, 501H, 502H from Nippon Kayaku Co., Ltd., EOCN-102S, 103S, 104S, 1020 from Japan Epoxy Resin Co., Ltd., Epicote 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 from Daicel Chemical Industries, Ltd., Celoxide 2021 from Daicel Chemical Industries, Ltd., EHPE-3150 from Daicel Chemical Industries, Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 from Nagase ChemteX Corporation, TEPIC-L, H, S from Nissan Chemical Industries, Ltd., EPICLON from DIC Corporation Examples include 830, 840, 850, 860, 1050, 3050, 4050, N-660, N-670, N-740, N-770, N865, HP-7200, HP-4700, HP-4770, HP-5000, HP-6000, HP-9500, etc.

[0166] The epoxy compound content is preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0167] (Oxetane compounds) Oxetane compounds are known compounds that have an oxetane group. Examples of oxetane compounds include monofunctional oxetane compounds, difunctional oxetane compounds, and trifunctional or multifunctional oxetane compounds.

[0168] Examples of monofunctional oxetane compounds include (3-ethyloxetane-3-yl)methyl acrylate, (3-ethyloxetane-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.

[0169] Examples of bifunctional oxetane compounds 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, ethylene glycos(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl(3-ethyl- Examples include 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.

[0170] Examples of oxetane compounds with three or more functionalities include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether. Examples include ethyl(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis(3-ethyl-3-oxetanylmethyl) ether, and resins containing oxetane groups (for example, oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462).

[0171] Examples of commercially available oxetane compounds include OXBP and OXTP manufactured by Ube Industries, Ltd., OXE-10 and 30 manufactured by Osaka Organic Chemical Industry Co., Ltd., and OXT-101 and 212 manufactured by Toagosei Co., Ltd.

[0172] The oxetane compound content is preferably 0.5 to 50% by mass, and more preferably 1 to 40% by mass, based on 100% by mass of the nonvolatile content of the photosensitive colored composition.

[0173] Melamine compounds are compounds having a melamine ring structure. Methylol-type and ether-type melamine compounds are preferred, and melamine compounds with an average of 5.0 or more methylol groups and / or ether groups per melamine ring are more preferred. Having a moderate number of methylol groups and / or ether groups makes it easier to obtain adequate heat resistance.

[0174] Examples of commercially available melamine compounds include 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, and MX-410 from Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 from Nippon Cytec Industries Co., Ltd.

[0175] 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 from Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 300, 301, 303, 350 from Nippon Cytec Industries Co., Ltd. are preferred in that they can increase the crosslinking density, as they have an average of 5.0 or more methylol groups and / or ether groups per melamine ring.

[0176] Thermosetting compound (I) can be used alone or in combination of two or more types.

[0177] [Hardening agent (hardening accelerator)] The photosensitive colored composition of the present invention may contain a curing agent (curing accelerator) to assist in the curing of the thermosetting compound (I).

[0178] Examples of curing agents include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, sulfonic acid compounds, etc. 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, Examples include 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., phosphorus compounds (e.g., triphenylphosphine), 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.).

[0179] The hardening agent can be used alone or in combination of two or more types.

[0180] The curing agent content is preferably 0.01 to 15 parts by mass per 100 parts by mass of thermosetting compound (I).

[0181] [Thiol-based chain transfer agent (J)] The photosensitive coloring composition of the present invention may contain a thiol-based chain transfer agent (J).

[0182] When used in combination with a polymerization initiator (D), the thiol chain transfer agent (J) generates thiyl radicals that are less susceptible to polymerization inhibition by oxygen during radical polymerization after light irradiation, thereby improving the photosensitivity of the photosensitive colored composition.

[0183] The thiol-based chain transfer agent (J) is preferably a polyfunctional thiol having two or more thiol groups (SH groups). More preferably, the thiol-based chain transfer agent has four or more SH groups. As the number of functional groups increases, photocuring becomes easier from the surface to the deepest part of the film.

[0184] Polyfunctional thiols include, for example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol Examples include lithritol 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.

[0185] Thiol-based chain transfer agents (J) can be used alone or in combination of two or more types.

[0186] The content of the thiol chain transfer agent (J) is preferably 1 to 10% by mass, and more preferably 2 to 8% by mass, based on 100% by mass of the nonvolatile content of the photosensitive colored composition.

[0187] [Polymerization inhibitor (K)] The photosensitive colored composition of the present invention may contain a polymerization inhibitor (K).

[0188] Polymerization inhibitor (K) is, for example, 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-t-butylcatechol, 3-t-butylcatechol, 4-t-butylcatechol, 3,5-di-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n Examples include alkylresorcinol compounds such as -butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, and 2,5-di-t-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and trybenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphine and trisnonylphenylphosphine; pyrogallol and phloroglucin.

[0189] The polymerization inhibitor (K) content is preferably 0.01 to 0.4% by mass of 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0190] [UV absorber (L)] The photosensitive colored composition of the present invention may contain an ultraviolet absorber (L).

[0191] The ultraviolet absorber (L) is an organic compound that has ultraviolet absorption function, and examples include benzotriazole organic compounds, triazine organic compounds, benzophenone organic compounds, salicylate ester organic compounds, cyanoacrylate organic compounds, and salicylate organic compounds.

[0192] Benzotriazole compounds include, for example, 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-t-octylphenyl)benzotriazole, and 5% 2-methoxy-1-methylphenyl A mixture of tyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazole2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl ester, 2-(2H-benzotriazole2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazole2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl3-(3-(2H-benzotriazole2-yl) Reaction product of (-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazole2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazole2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazole2-yl)-6-t-butyl-4-methylpheno Examples include 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-benzotriazole2-yl)phenyl]propionate, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazole2-yl)phenyl]propionate.

[0193] Examples of commercially available products include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 from BASF Japan; 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.

[0194] Triazine compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of the resulting compounds 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.

[0195] Examples of commercially available products include KEMISORB102 from Chemipro Chemical Co., Ltd., TINUVIN400, 405, 460, 477, 479, and 1577ED from BASF Japan, ADEKA LA-46 and LA-F70 from ADEKA, and CYASORB UV-1164 from Sun Chemical Co., Ltd.

[0196] Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid 3-hydrobenzophenone, 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.

[0197] Examples of commercially available products include KEMISORB10, 11, 11S, 12, and 111 from Chemipro Chemical Co., Ltd., SEESORB101 and 107 from Cipro Chemical Co., Ltd., ADEKA Stab 1413 from ADEKA Corporation, and UV-12 from Sun Chemical Co., Ltd.

[0198] Examples of salicylate ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0199] The amount of ultraviolet absorber (L) is preferably 5 to 70% by mass of the total mass of polymerization initiator (D) and ultraviolet absorber (L).

[0200] [Antioxidant (M)] The photosensitive colored composition of the present invention may contain an antioxidant (M).

[0201] Examples of antioxidants (M) include hindered phenol, hindered amine, phosphorus, sulfur, and hydroxylamine compounds. In this invention, the antioxidant is preferably a compound that does not contain halogen atoms.

[0202] Among these, hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferred.

[0203] Hindered phenol antioxidants, for example, 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-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5] Undecane, 1,3,5-Tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-Tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-Methylenebis(6-t-butyl-4-ethylphenol), 2,2'-Thiodiethylbis-(3,5-di -t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxyhydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4 ,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanediolbis[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.

[0204] Examples of commercially available products include ADEKA's ADEKA stub AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330; Chemipro's KEMINOX 101, 179, 76, 9425; BASF Japan's IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565; and Sun Chemical's Cyanox CY-1790, CY-2777.

[0205] Hindered amine antioxidants include, for example, 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-pentamethyl-4-piperidyl. Tamethyl-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- Ester of piperidineethanol 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, bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester of decandioate, reaction product of 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.

[0206] Examples of commercially available products include ADEKA's ADEKA Stab LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, LA-502XP; KAMISTAB29, 62, 77, 94 from Chemipro Chemical; Tinuvin111FDL, 123, 144, 249, 292, 5100 from BASF Japan; and Siasorb UV-3346, UV-3529, UV-3853 from Sun Chemical.

[0207] Phosphorus-based antioxidants include, for example, 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-biphenyldiphosphonate, 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)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)benzene, and ethylbis(2,4-di-t-butyl-6-methylphenyl) phosphite.

[0208] Examples of commercially available products include ADEKA's ADEKA Stub PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP; BASF Japan's IRGAFOS168; and Clariant Chemicals' Hostanox P-EPQ.

[0209] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

[0210] Examples of commercially available products include ADEKA's ADEKA stub AO-412S and AO-503, and KEMINOXPLS from Chemipro Chemical Co., Ltd.

[0211] Antioxidants (M) can be used alone or in combination of two or more types.

[0212] The antioxidant (M) content is preferably 0.5 to 5.0% by mass of 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0213] [Leveling agent (N)] The photosensitive colored composition of the present invention may contain a leveling agent (N).

[0214] Examples of leveling agents (N) include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0215] Silicone-based surfactants include, for example, linear polymers composed of siloxane bonds, and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0216] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 from Bic Chemie, and FZ-7002, 211 from Toray Dow Corning. Examples include 0, 2122, 2123, 2191, 5609, and Shin-Etsu Chemical Co., Ltd.'s X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

[0217] Examples of fluorinated surfactants include surfactants or leveling agents having fluorocarbon chains.

[0218] Examples of commercially available products include Surflon S-242, 243, 420, 611, 651, and 386 from AGC Seimi Chemical; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, as well as R-40-LM, R-41, RS-72-K, and DS-21 from DIC; FC-4430 and 4432 from Sumitomo 3M; EF-PP31N09, EF-PP33G1, and EF-PP32C1 from Mitsubishi Materials Electronic Chemicals; and Futergent 602A from Neos.

[0219] Nonionic surfactants include, for example, 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 tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, 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.

[0220] Commercially available products include, for example, 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, L S-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, 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- L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amit 102, Examples include 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA's Adekapluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R, and Kyoeisha Chemical's (meth)acrylic acid-based (co)polymer Polyflow-No.75, No.90, No.95.

[0221] Cationic surfactants include, for example, alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and their ethylene oxide adducts.

[0222] Examples of commercially available products include Acetamine 24, Cotamin 24P, 60W, and 86P Concentrate, all manufactured by Kao Corporation.

[0223] 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.

[0224] Examples of commercially available products include Neos's Futergent 100 and 150, and ADEKA's Adeka Hope YES-25, Adeka Call TS-230E, PS-440E, and EC-8600.

[0225] 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.

[0226] Examples of commercially available products include Anchitol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, ​​and 20N, manufactured by Kao Corporation.

[0227] Leveling agent (N) can be used alone or in combination of two or more types.

[0228] The leveling agent (N) content is preferably 0.001 to 2.0% by mass, and more preferably 0.005 to 1.0% by mass, based on 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0229] [Storage stabilizer (O)] The photosensitive colored composition of the present invention may contain a storage stabilizer (O).

[0230] Storage stabilizers (O) include, for example, benzyltrimethyl chloride, quaternary ammonium chlorides such as diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organophosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl, and phosphates.

[0231] The storage stabilizer (O) content is preferably 0.1 to 10 parts by mass per 100 parts by mass of coloring agent (A).

[0232] [Adhesion enhancer (P)] The photosensitive colored composition of the present invention may contain an adhesion enhancer (P).

[0233] The adhesion enhancer (P) is, for example, vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acryloxysilanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; and N-2-(aminoethyl)-3-aminopropylmethyl Examples include dimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethylbutylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, aminosilanes such as hydrochloride salt of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureidos such as 3-ureidopropyltriethoxysilane, and isocyanates such as 3-isocyanatetopropyltriethoxysilane.

[0234] Adhesion enhancers (P) can be used alone or in combination of two or more types.

[0235] The content of the adhesion enhancer (P) is preferably 0.1 to 5.0% by mass of 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0236] [Organic solvent (Q)] The photosensitive composition of the present invention may contain an organic solvent (Q).

[0237] Organic solvent (Q) is, 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 Tyl 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, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, 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, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate,Examples include 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.

[0238] From an environmental standpoint, the photosensitive coloring composition of the present invention preferably contains substantially no organic solvents, such as aromatic hydrocarbons (toluene, xylene, benzene, chlorobenzene, etc.). Substantially no organic solvents means that the concentration is 50 ppm by mass or less, preferably 30 ppm by mass or less, and more preferably 10 ppm by mass or less in the photosensitive coloring composition.

[0239] Organic solvent (Q) can be used alone or in combination of two or more types.

[0240] The amount of organic solvent (Q) is preferably such that the non-volatile content of the photosensitive coloring composition is 5 to 70% by mass.

[0241] [Water content] From the viewpoint of storage stability, the photosensitive coloring composition of the present invention preferably contains 2.0% by mass or less of water.

[0242] The water content in the photosensitive coloring composition is more preferably 1.5% by mass or less, and particularly preferably 1.0% by mass or less. Also, the lower limit of the water content is not particularly limited.

[0243] The method for controlling the water content is not particularly limited, and known methods can be used. For example, each of the above-described components is sufficiently dried, etc., and those with a reduced water content in the components are used. Also, methods such as manufacturing the photosensitive coloring composition while blowing dry air, an inert gas, or a mixed gas thereof, and a method of adding molecular sieves for dehydration after manufacturing can be mentioned.

[0244] The water content can be measured by a known method such as the Karl Fischer method.

[0245] [Method for producing a photosensitive coloring composition] The photosensitive coloring composition of the present invention can be prepared by mixing the above-described components. At the time of preparation, the components may be compounded together, or may be sequentially compounded after dissolving or dispersing each component in an organic solvent. For example, a dispersion is produced by adding a colorant (A), an alkali-soluble resin (B), an organic solvent (P), etc. and performing a dispersion treatment. Thereafter, it can be produced by compounding and mixing a polymerizable compound (C), a polymerization initiator (D), and a compound (E) represented by the general formula (1) to the dispersion. Note that the timing of compounding each material is arbitrary. Also, the dispersion step can be performed multiple times.

[0246] Examples of the disperser for performing the dispersion treatment include 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, etc.

[0247] The average dispersed particle diameter (secondary particle diameter) of the colorant (A) in the photosensitive coloring composition is preferably 30 to 200 nm, and more preferably 40 to 200 nm. When it has an appropriate particle diameter, it is easy to obtain a photosensitive coloring composition with high dispersion stability.

[0248] The method for measuring the average dispersed particle diameter (secondary particle diameter) employs, for example, the Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd. that adopts the dynamic light scattering method (FFT power-spectrum method). The particle permeability is set to the absorption mode, the particle shape is set to non-spherical, and the D50 particle diameter is set as the average diameter. For the dilution solvent used for measurement, the organic solvents used for dispersion are respectively used. When measuring the sample immediately after sample adjustment for the sample treated with ultrasonic waves, results with less variation are easily obtained and are preferable.

[0249] The photosensitive coloring composition is preferably subjected to removal of coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and mixed dust by means such as centrifugation, filtration using a sintered filter or a membrane filter. The photosensitive coloring composition of the present invention preferably contains substantially no particles of 0.5 μm or more, and more preferably contains no particles of 0.3 μm or less.

[0250] <Film> The film of the present invention is formed using the above-described photosensitive coloring composition. A film having a pattern is preferable as the film, but it can also be used as a flat film.

[0251] [Method for manufacturing film] The method for manufacturing the film is not particularly limited, and known methods can be used. For example, it can be manufactured through a process of coating the photosensitive coloring composition of the present invention on a substrate.

[0252] Examples of the substrate include a substrate made of a material such as glass, resin, or silicon. An organic light-emitting layer may be formed on these substrates. Further, an imaging element such as a CCD or a CMOS may be formed on the substrate. Further, a primer layer may be provided on the substrate, if necessary, for improving adhesion to an upper layer, preventing diffusion of substances, and planarizing the substrate surface.

[0253] Known coating methods can be used. Examples thereof include a dropping method, a slit coating method, a spraying method, a roll coating method, a spin coating method, a casting coating method, an inkjet method, flexographic printing, screen printing, gravure printing, offset printing, and the like.

[0254] The film thickness can be adjusted as appropriate depending on the purpose. A film thickness of 0.05 to 20.0 μm is preferred, and 0.3 to 10.0 μm is more preferred.

[0255] Next, a pattern is formed. Methods for forming the pattern include photolithography and dry etching, with photolithography being preferred. However, when used as a flat film, the pattern formation step is not necessary; after coating, drying and exposure of the entire surface are performed as needed.

[0256] The following describes in detail how to form the patterns.

[0257] When forming a pattern using photolithography, the photosensitive coloring composition of the present invention is coated onto a substrate to form a layer. After pre-baking as necessary, the layer is exposed to light in a patterned manner through a mask (exposure step). Unexposed areas are removed by alkaline development (development step), and then the pattern is heat-treated (post-bake step).

[0258] [Exposure process] The exposure process involves exposing a layer formed by coating to a specific pattern via a mask using an exposure device such as a stepper. This allows the exposed area to harden. Examples of active energy rays used for exposure include ultraviolet rays such as g-rays (wavelength 436 nm), h-rays (wavelength 405 nm), and i-rays (wavelength 365 nm). Light with a wavelength of 300 nm or less can also be used. Examples of light with a wavelength of 300 nm or less include KrF-rays (wavelength 248 nm) and ArF-rays (wavelength 193 nm). Furthermore, exposure may be performed by continuously irradiating with light, or by repeatedly irradiating and pausing with light in short cycles (for example, at the millisecond level or less) (pulsed exposure).

[0259] [Development process] Next, by performing an alkaline development treatment, the unexposed layers dissolve in the alkaline aqueous solution, leaving only the hardened parts and obtaining a patterned film. Examples of alkaline developers include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, and more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, and more preferably 11.5 to 12.5. Using an appropriate pH suppresses pattern roughness and peeling, and improves the residual film rate after development. Development methods include, for example, the dip method, spray method, and paddle method. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

[0260] [Post-baking process] After development, a heat treatment (post-bake) is performed. Post-bake improves the durability of the film. The temperature is preferably between 80 and 300°C. The duration is preferably between 2 minutes and 1 hour. When a material with low heat resistance is used as the substrate, or when a substrate having an organic electroluminescent element as the light-emitting layer is used, the temperature is preferably 150°C or lower, and more preferably 130°C or lower.

[0261] <Color Filter> The film of the present invention can be used in color filters. The color filters of the present invention can be used in solid-state image sensors such as CCDs and CMOS sensors, and image display devices. By appropriately selecting a coloring agent (A), red color filters, green color filters, blue color filters, magenta color filters, cyan color filters, yellow color filters, gray color filters, black color filters, etc., can be obtained. The color filters can be manufactured in the same manner as the film described above.

[0262] <Solid-state image sensor> The film of the present invention can be used in solid-state image sensors. The form in which it is used in solid-state image sensors is not particularly limited, but for example, a substrate has a plurality of photodiodes and transfer electrodes made of polysilicon or the like that constitute the light-receiving area of ​​a solid-state image sensor (CCD image sensor, CMOS image sensor, etc.), a light-shielding film has an opening only for the light-receiving portion of the photodiode on the photodiode and transfer electrode, a device protection film made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiode, and a filter has a filter on the device protection film. Furthermore, a configuration in which a light-gathering means (e.g., a microlens, etc.; the same applies hereinafter) is provided on the device protection film below the filter (closer to the substrate), or a configuration in which the light-gathering means is provided on the filter, etc. The filter may also have a structure in which the film of the present invention that forms each colored pixel is embedded in a space partitioned, for example, in a grid pattern by partitions. In this case, it is preferable that the partitions have a low refractive index with respect to each colored pixel. The imaging device equipped with the solid-state image sensor of the present invention can be used in a variety of applications, such as digital cameras, electronic devices with imaging capabilities (smartphones, tablet devices, etc.), in-vehicle cameras, surveillance cameras, and sensors.

[0263] <Image display device> The film of the present invention can be used in image display devices. Examples of image display devices include liquid crystal displays and organic EL displays. The form in which it is used in image display devices is not particularly limited, but it can be used as a color filter or a black matrix. The form used in the image display device is not particularly limited, as long as it functions as an image display device. For example, the configuration described in "Next-Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994) is one such example. For definitions of image display devices and details of various image display devices, see, for example, "Electronic Display Devices" (by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990) and "Display Devices" (by Junsho Ibuki, Sangyo Tosho Co., Ltd., published in 1989). [Examples]

[0264] The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited thereto. Note that "parts" means "parts by mass" and "%" means "% by mass". In the present invention, the non-volatile content or non-volatile content concentration refers to the mass residue after oven standing at 230°C for 30 minutes.

[0265] Prior to the examples, each measurement method will be described.

[0266] (Average molecular weight of resin) 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 RI detector. As the apparatus, HLC-8220GPC (manufactured by Tosoh Corporation) was used. Two separation columns were connected in series, and for both fillers, "TSK-GEL SUPER HZM-N" was connected in a pair and used. The oven temperature was 40°C, a tetrahydrofuran (THF) solution was used as the eluent, and the measurement was performed at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent composed of 1% by mass of the above eluent, and 20 microliters were injected. The molecular weight is a polystyrene equivalent value.

[0267] (Acid value of resin) 80 ml of acetone and 10 ml of water were added to 0.5 - 1 g of the resin solution, and the mixture was stirred until uniformly dissolved. Using a 0.1 mol / L aqueous KOH solution as the titrant, titration was performed using an automatic titrator ("COM-555", manufactured by Hiranuma Sangyo Co., Ltd.), and the acid value (mgKOH / g) was measured. Then, from the acid value of the resin solution and the non-volatile content concentration of the resin solution, the acid value per non-volatile content of the resin was calculated.

[0268] (Amine value of resin) The amine value of the resin is a value obtained by converting the total measured amine value (mgKOH / g) to a non-volatile content basis in accordance with the method of ASTM D 2074.

[0269] (Production of colorant (A)) (Colorant (A-7)) In accordance with the description in Japanese Patent Publication No. 2014-12838, a coloring agent (A-7) was obtained containing an azo compound represented by general formula (2) and an anion of the azo compound having a tautomer structure thereof, and a compound represented by general formula (3), with a molar ratio of Ni and Zn metal ions of 65:35.

[0270] <Manufacturing of alkali-soluble resin (B)> (Alkali-soluble resin (B1-1) containing hydroxyl group monomer units (b1)) A reaction vessel was prepared by fitting a thermometer, condenser, nitrogen gas inlet tube, and stirrer into a separable four-neck flask. 100 parts of propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMAc) were placed in the vessel, and the vessel was heated to 120°C while nitrogen gas was injected into it. At the same temperature, a mixture of 56.86 parts (0.4 mol) of glycidyl methacrylate, 66.09 parts (0.3 mol) of dicyclopentanyl methacrylate, and 31.25 parts (0.3 mol) of styrene, along with a polymerization initiator dissolved in 5.0 parts of PGMAc, was added dropwise over 2.5 hours to carry out the polymerization reaction. After the dropwise addition was complete, the mixture was stirred at 120°C for a further 2 hours to obtain the precursor. Next, the flask was purged with air, and 28.82 parts (0.4 moles) of acrylic acid, 0.3 parts of trisdimethylaminomethylphenol, and 0.3 parts of hydroquinone were added as the modified compound, and the mixture was reacted at 120°C for 5 hours. This reacted the epoxy group of glycidyl methacrylate with the carboxyl group of acrylic acid, causing the epoxy group of glycidyl methacrylate to cleave and generate a hydroxyl group, while simultaneously introducing a polymerizable unsaturated group. Next, 48.68 parts (0.32 moles) of tetrahydrophthalic anhydride and 0.5 parts of triethylamine were added as modifying compounds and reacted at 120°C for 4 hours. This caused some of the hydroxyl groups generated by the cleavage of the epoxy group of glycidyl methacrylate to react with tetrahydrophthalic anhydride, introducing carboxyl groups. Subsequently, PGMAc was added to achieve a non-volatile content of 20% by mass to prepare an alkali-soluble resin (B1-1) having a hydroxyl group-containing monomer unit (b1). The weight-average molecular weight (Mw) was 10,000 and the acid value was 77 mgKOH / g.

[0271] (Alkali-soluble resins (B1-2) to (B1-6) containing hydroxyl group monomer units (b1)) Alkali-soluble resins (B1-2) to (B1-6) containing hydroxyl group monomer units (b1) were synthesized by changing the types and amounts of compounds to match the components and composition ratios shown in Table 1, and PGMAc was added to bring the non-volatile content to 20% by mass.

[0272] [Table 1]

[0273] The Arronix M-110 listed in Table 1 is paracumylphenol ethylene oxide modified acrylate manufactured by Toagosei Co., Ltd., and the Karenz MOI-DEM is malonate-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester manufactured by Showa Denko Corporation.

[0274] (Alkali-soluble resin (B2-1) that does not contain hydroxyl group-containing monomer units (b1)) 160 parts of PGMAc were placed in a reaction vessel, which was a separable four-neck flask fitted with a thermometer, condenser, nitrogen gas inlet tube, and stirrer. The vessel was heated to 120°C while nitrogen gas was injected into it. At the same temperature, 109.25 parts (0.62 mol) of benzyl methacrylate, 24.1 parts (0.28 mol) of methacrylic acid, 22.03 parts (0.1 mol) of dicyclopentanyl methacrylate, 1.0 part of the polymerization initiator azobisisobutyronitrile, and a mixture of PGMAc were added dropwise over 2.5 hours using a dropping tube. After the dropwise addition was complete, the mixture was stirred at 120°C for a further 2 hours. Subsequently, PGMAc was added to achieve a non-volatile content of 20% by mass to prepare an alkali-soluble resin (B2-1) that does not contain hydroxyl group-containing monomer units (b1). The weight-average molecular weight was 17,500 and the acid value was 98 mgKOH / g.

[0275] <Production of polymerizable compound (C)> (Polymerizable compound containing urethane bonds (C3-1)) In a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube, 400 parts pentaerythritol triacrylate, 100 parts PGMAc, and 0.5 parts N,N-dimethylbenzylamine were charged. The temperature was raised to 70°C, and a mixture of 112 parts hexamethylene diisocyanate and 112 parts PGMAc was added dropwise from the dropping tube over 2 hours. After addition, the mixture was reacted at a temperature of 50-70°C for 8 hours, and IR measurements were taken at 2,180 cm³. -1 The disappearance of the absorption of the isocyanate was confirmed. PGMAc was added to achieve a non-volatile content of 50% by mass, yielding a polymerizable compound (C3-1) having a urethane bond with an average of 6 polymerizable unsaturated groups.

[0276] (Polymerizable compound (C3-2) containing urethane bonds) In a five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine were charged. The temperature was raised to 70°C, and a mixture of 64 parts of hexamethylene diisocyanate and 64 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After addition, the mixture was reacted at a temperature of 50-70°C for 8 hours, and the reaction was measured at 2,180 cm³ by infrared radiation. -1 The disappearance of the absorption of the isocyanate was confirmed. PGMAc was added to achieve a non-volatile content of 50% by mass, yielding a polymerizable compound (C3-2) having urethane bonds with an average of 10 polymerizable unsaturated groups.

[0277] (Polymerizable compound (C3-3) containing urethane bonds) A five-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube was charged with 400 parts dipentaerythritol pentaacrylate, 100 parts PGMAc, and 0.5 parts N,N-dimethylbenzylamine. The temperature was raised to 70°C, and a mixture of 66 parts toluene diisocyanate and 66 parts PGMAc was added dropwise from the dropping tube over 2 hours. After addition, the mixture was reacted at a temperature of 50-70°C for 8 hours, and the reaction was measured at 2,180 cm³ by infrared radiation. -1The disappearance of the absorption of the isocyanate was confirmed. Next, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged and reacted at a temperature of 50-60°C for 6 hours. The non-volatile content was adjusted to 50% by mass to obtain a polymerizable compound (C3-3) having an average of 9 polymerizable unsaturated groups, acidic groups, and urethane bonds.

[0278] <Manufacturing of Dispersed Resin (G)> (Dispersed resin (G-1)) In a reaction vessel equipped with a gas inlet tube, temperature control, condenser, and stirrer, 10 parts methacrylic acid, 100 parts methyl methacrylate, 70 parts iso-butyl methacrylate, 20 parts benzyl methacrylate, and 50 parts PGMAc were charged and purged with nitrogen gas. The reaction vessel was heated to 50°C and stirred, and 12 parts 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 2,2'-azobisisobutyronitrile added to 90 parts PGMAc. Non-volatile content measurement confirmed that 95% had reacted. 19 parts pyromellitic anhydride, 50 parts PGMAc, 50 parts cyclohexanone, and 0.4 parts 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100°C for 7 hours. After confirming that over 98% of the acid anhydride had undergone half-esterification by measuring the acid value, the reaction was terminated, and PGMAc was added to obtain dispersion resin (G-1) with a non-volatile content of 30% by mass. The acid value was 70 mgKOH / g.

[0279] (Dispersed resin (G-2)) In a reactor equipped with a gas inlet pipe, condenser, stirring blades, and thermometer, 40 parts methyl methacrylate, 10 parts n-butyl methacrylate, and 13.2 parts tetramethylethylenediamine as catalyst were charged, and the mixture was stirred at 50°C for 1 hour while flowing nitrogen, and the system was purged with nitrogen. Next, 9.3 parts ethyl bromoisobutyrate as initiator, 5.6 parts cuprous chloride as catalyst, and 100 parts PGMAc were charged, and the temperature was raised to 110°C under a nitrogen atmosphere to start polymerization of the first block (block B). After 4 hours of polymerization, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or higher based on the non-volatile content. Next, 50 parts PGMAc, 40 parts dimethylaminoethyl methacrylate and 10 parts methacryloyloxyethyl benzyldimethylammonium chloride as monomers for the second block (block A) were added to this reactor, and the reaction was continued by stirring while maintaining 110°C and a nitrogen atmosphere. Two hours after the start of the reaction, the polymerization solution was sampled and its non-volatile content was measured. Based on the non-volatile content, it was confirmed that the polymerization conversion rate of the second block (block A) was 98% or higher, and the reaction solution was cooled to room temperature to stop the polymerization. After cooling to room temperature, approximately 2 g was sampled and heated and dried at 180°C for 20 minutes, and the non-volatile content was measured. PGMAc was added to obtain dispersed resin (G-2) so that the non-volatile content was 30% by mass. The amine value was 169.8 mgKOH / g.

[0280] <Dispersion manufacturing> (Dispersion 1) After stirring and mixing the following raw materials until uniform, the mixture was dispersed for 3 hours using an Eiger mill (Eiger Japan's "Mini Model M-250 MKII") with a 0.5 mm diameter zirconia bead, and then filtered through a 1.0 μm pore size filter to prepare dispersion 1. Coloring agent (A-1): 15.0 parts Dispersion resin (G-2): 15.0 parts Organic solvent (Q-1): 70.0 parts

[0281] (Dispersion 2~13) Dispersions 2-13 were prepared in the same manner as dispersion 1, except that the components and quantities listed in Table 2 were changed.

[0282] [Table 2-1]

[0283] [Table 2-2]

[0284] The components listed in Tables 2-1 and 2-2 are as follows:

[0285] [Coloring agent (A)] A-1: CI Pigment Green 58 A-2: CI Pigment Green 59 A-3: CI Pigment Green 63 A-4: CI Pigment Yellow 138 A-5: CI Pigment Yellow 139 A-6: CI Pigment Yellow 150 A-8: CI Pigment Red 254 A-9: CI Pigment Red 177 A-10: CI Pigment Blue 15:3 A-11: CI Pigment Blue 15:6 A-12: CI Pigment Violet 23 A-13: Carbon Black

[0286] [Dye derivative (F)] [ka]

[0287] [Organic solvent (Q)] Q-1: Propylene glycol monomethyl ether acetate

[0288] <Manufacturing of photosensitive colored compositions> [Example 1] (Photosensitive coloring composition 1) The following raw materials were mixed and stirred, and filtered through a filter with a pore size of 1.0 μm to obtain photosensitive colored composition 1. Dispersion 1: 30.0 parts Dispersion 4: 10.0 parts Alkali-soluble resin (B1-1) having a hydroxyl group-containing monomer unit (b1) :12.0 copies Alkali-soluble resin (B2-1) that does not have hydroxyl group-containing monomer units (b1) : 5.0 copies Polymerizable compound (C3-2) containing urethane bonds: 1.6 parts Polymerizable compound (C3-3) containing urethane bonds: 3.6 parts Other polymerizable compounds (C7-1): 3.2 parts Polymerization initiator (D-1): 0.5 parts Compound (E-1) represented by general formula (1): 5.0 parts Leveling agent (N): 1.0 part Organic solvent (Q-1): 18.1 parts Organic solvent (Q-2): 10.0 parts

[0289] [Examples 2-43, and Comparative Examples 1 and 2] (Photosensitive coloring composition 2-45) Photosensitive colored compositions 2 to 45 were prepared in the same manner as in Example 1, except that the raw materials and quantities of photosensitive colored composition 1 from Example 1 were changed to those listed in Tables 3-1 to 3-5.

[0290] [Table 3-1]

[0291] [Table 3-2]

[0292] [Table 3-3]

[0293] [Table 3-4]

[0294] [Table 3-5]

[0295] The ingredients listed in Tables 3-1 to 3-5 are as follows:

[0296] [Polymerizable compound (C)] C1-1: Dipentaerythritol pentaacrylate C2-1: Arronix M-520 (manufactured by Toagosei Co., Ltd.) C4-1: KAYARAD DCPA-30 (manufactured by Nippon Kayaku Co., Ltd.) C7-1: Dipentaerythritol hexaacrylate [Polymerization initiator (D)] D-1: Compound (D-1) described above D-2: Compound (D-2) described above D-3: Compound (D-3) described above D-4: Compound (D-4) described above D-5: Compound (D-5) described above D-6: Omnirad 907 (manufactured by IGM Resins) D-7: The following compounds

[0297] [ka]

[0298] [Compound represented by general formula (1) (E)] E-1: 10% PGMac solution of the compound (E-1) described above. E-2: 10% PGMac solution of the compound (E-2) described above. E-3: 10% PGMac solution of the compound (E-3) described above. E-7: 10% PGMac solution of the compound (E-7) described above.

[0299] [Leveling agent (N)] One part each of BYK-330 (manufactured by Big Chemie) and Megafac F-551 (manufactured by DIC) were mixed and dissolved in 98 parts of PGMAc to create a mixed solution which was used as the leveling agent (N).

[0300] [Adhesion enhancer (P)] 3-Glycidoxypropyltrimethoxysilane

[0301] [Organic solvent (Q)] Q-1: Propylene glycol monomethyl ether acetate Q-2:3-Ethyl ethoxypropionate

[0302] <Evaluation of photosensitive colored compositions> The photosensitive colored compositions 1 to 45 obtained were evaluated for adhesion, pattern shape, surface smoothness, and developability after storage using the following methods. The evaluation results are shown in Table 4.

[0303] [Adhesion evaluation] The obtained photosensitive colored composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) by spin coating to a dry film thickness of 2.0 μm, and dried on a hot plate at 70°C for 1 minute. Next, after the substrate cooled to room temperature, it was illuminated at 30 mW / cm² using a high-pressure mercury lamp through a photomask with a stripe pattern of 5 μm widths. 2 50 mJ / cm² 2 The substrate was exposed to light. Subsequently, this substrate was spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C, washed with deionized water, air-dried, and heated in a clean oven at 230°C for 30 minutes to obtain an evaluation substrate. Spray development was performed for the shortest possible time that allowed for pattern formation without any remaining development on the film of each photosensitive coloring composition, and this was defined as the appropriate development time. Fine line patterns with a width of 5 to 25 μm on the evaluation substrate were observed using an optical microscope to confirm the remaining fine line patterns. The evaluation criteria are as follows, with a score of 3 or higher indicating practical usability. 5: Fine lines smaller than 10 μm remain. 4: Fine lines larger than 15 μm remain. 3: Fine lines larger than 20 μm remain. A fine line measuring 2:25 μm remains. 1: No thin lines remain.

[0304] [Pattern shape evaluation (1): Linearity] The obtained photosensitive colored composition was coated onto a 100 mm x 100 mm, 0.7 mm thick glass substrate (Corning Eagle 2000) by spin coating to a dry film thickness of 2.0 μm, and dried on a hot plate at 70°C for 1 minute. After the substrate cooled to room temperature, it was illuminated using an ultra-high pressure mercury lamp at an illuminance of 30 mW / cm². 2 50 mJ / cm² 2 The substrate was then exposed to ultraviolet light through a photomask with a 100 μm wide stripe pattern. Subsequently, the substrate was spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C, washed with deionized water, air-dried, and heated in a clean oven at 230°C for 30 minutes to obtain an evaluation substrate. Spray development was performed for the shortest possible time that allowed for pattern formation without any remaining development for each photosensitive coloring composition, and this was defined as the appropriate development time. The evaluation substrate was performed by measuring the maximum and minimum line widths of 10 stripe patterns using a Nikon ECLIPSE LV100POL Model optical microscope and calculating the average. The evaluation criteria were as follows, with a score of 3 or higher indicating practical usability. 5: The difference between the maximum and minimum line widths is less than 0.5 μm. 4: The difference between the maximum and minimum line widths is 0.5 μm or more, and less than 1.0 μm. 3: The difference between the maximum and minimum line widths is 1.0 μm or more, and less than 1.5 μm. 2: The difference between the maximum and minimum line widths is 1.5 μm or more, and less than 2.0 μm. 1: The difference between the maximum and minimum line widths is 2.0 μm or more

[0305] [Pattern shape evaluation (2): Cross-sectional shape] Using a scanning electron microscope (Hitachi High-Technologies Corporation's "S-3000H"), the cross-sectional shape of the pattern was confirmed on the substrate created in Pattern shape evaluation (1). The evaluation was performed by capturing the SEM image of the cross-section of the pattern and measuring the taper angle between the base material and the end of the pattern cross-section. The evaluation criteria are as follows, and a value of 3 or more is considered practical. 5: Taper angle is 30 degrees or more and less than 50 degrees 4: Taper angle is 50 degrees or more and less than 60 degrees 3: Taper angle is less than 30 degrees or 60 degrees or more and less than 70 degrees 2: Taper angle is 70 degrees or more and less than 90 degrees 1: Taper angle is 90 degrees or more

[0306] [Surface smoothness evaluation] Using an optical microscope (Olympus Optical Co., Ltd.'s "BX-51", magnification: 200 times), the surface of the pattern was confirmed on the substrate created in Pattern shape evaluation (1). A value of 3 or more is considered practical. 5: No wrinkles and unevenness are observed on the surface of the pattern. 4: Very slight wrinkles or unevenness are observed on the surface of the pattern. 3: Slight wrinkles or unevenness are observed on the surface of the pattern. 2: Wrinkles or unevenness are observed on the surface of the pattern. 1: Severe wrinkles and unevenness are observed on the surface of the pattern.

[0307] [Developability evaluation after storage] The obtained photosensitive coloring composition was applied by spin coating method onto a glass substrate (Corning's Eagle 2000) with a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm so that the dry film thickness became 2.0 μm, and dried on a hot plate at 70 °C for 1 minute. Then, after cooling this substrate to room temperature, using an ultra-high pressure mercury lamp, an illuminance of 2 30 mW / cm, 2 50 mJ / cmThe substrate was then exposed to ultraviolet light through a photomask with a 100 μm wide stripe pattern. Subsequently, the substrate was spray-developed using an aqueous developer containing 0.12% nonionic surfactant and 0.04% potassium hydroxide at 23°C, washed with deionized water, and air-dried. Spray development was performed for the shortest possible time that allowed for pattern formation without any remaining development for each photosensitive coloring composition, and this was defined as the initial development time. The photosensitive colored composition was placed in a sealed container and stored at 40°C for one week. It was then developed under the same conditions as the initial evaluation and evaluated according to the following criteria. A score of 3 or higher is considered usable. 5. The development time after storage is between 90% and 110% of the initial development time. 4. The development time after storage is between 80% and less than 90% of the initial development time, or between 110% and 120%. 3. The development time after storage is between 70% and 80% of the initial development time, or between 120% and 130%. 2: The development time after storage is between 60% and less than 70% of the initial development time, or between 130% and 140%. 1: The development time after storage is less than 60% of the initial development time or more than 140% of the initial development time.

[0308] [Table 4]

Claims

1. It comprises a coloring agent (A), an alkali-soluble resin (B), a polymerizable compound (C), a polymerization initiator (D), and a compound (E) represented by the following general formula (1). A photosensitive coloring composition comprising at least two compounds (E) represented by the general formula (1). General formula (1) 【Chemistry 1】 (In general formula (1), each R independently represents an alkyl group, L represents a divalent linking group, and n represents an integer from 2 to 10.)

2. The photosensitive coloring composition according to claim 1, comprising a compound (E) represented by the general formula (1) such that n = 2.

3. The photosensitive colored composition according to claim 2, wherein the content of the compound n=2 is 30% by mass or more in 100% by mass of the compound (E) represented by the general formula (1).

4. The photosensitive colored composition according to claim 1 or 2, wherein the alkali-soluble resin (B) comprises an alkali-soluble resin (B1) having a hydroxyl group-containing monomer unit (b1).

5. The photosensitive coloring composition according to claim 1 or 2, wherein the polymerizable compound (C) comprises a polymerizable compound (C1) having a hydroxyl group.

6. A film comprising the photosensitive coloring composition according to claim 1 or 2.

7. A color filter having the film described in claim 6.

8. A solid-state image sensor having the color filter described in claim 7.

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

Images