Photosensitive coloring composition for color filter, color filter, solid-state imaging device, liquid crystal display device, and infrared sensor

Abstract

To provide a photosensitive coloring composition for a color filter capable of forming coating with a smooth surface while suppressing the generation of striation and capable of forming a pattern that suppresses residue in unexposed portions.SOLUTION: A photosensitive coloring composition for a color filter comprises a colorant (A), a resin (B), a polymerizable monomer (C), a photopolymerization initiator (D), and a solvent (E). The solvent (E) contains a solvent (E1) satisfying the following conditions (1) and (2) in an amount of 0.5 to 15 mass% relative to 100 mass% of the photosensitive coloring composition, and a solvent (E2) satisfying the following conditions (3) and (4) in an amount of 15 to 80 mass% relative to 100 mass% of the photosensitive coloring composition. (1) A boiling point at atmospheric pressure (1013.25 hPa) is equal to or greater than 180°C and less than 250°C. (2) A vapor pressure at 20°C is equal to or greater than 1 Pa and less than 15 Pa. (3) The boiling point at the atmospheric pressure (1013.25 hPa) is equal to or greater than 120°C and less than 150°C. (4) The vapor pressure at 20°C is equal to or greater than 400 Pa and less than 1200 Pa.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a photosensitive coloring composition used for manufacturing a color filter.

Background Art

[0002] Color filters having pixels formed from a photosensitive coloring composition are used in optical devices such as solid-state imaging devices, liquid crystal display devices, and infrared sensors. When forming a film on a support having steps such as complex unevenness on the surface, there are problems such as the occurrence of radial streaks called striations on the surface, and it is difficult to form a film with a smooth surface. Patent Document 1 discloses a photosensitive coloring composition suitable for the die coating method containing a high-boiling solvent having a vapor pressure of 400 Pa or less at 20°C and a boiling point of 150°C or more at 1013.25 hPa. Further, Patent Document 2 discloses that by containing a solvent having a vapor pressure of 400 Pa or less at 25°C and a viscosity of 1.5 mPa·s or less measured by a Canon Fenske viscometer at 25°C, a thick film having a film thickness of 50 μm or more and a uniform film thickness can be formed on a large substrate having a diameter of 300 mm or more by the spin coating method.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Patent Document 2

Summary of the Invention

Problems to be Solved by the Invention

[0004] However, when forming a film on a support having steps such as complex unevenness on the surface, there are problems such as the occurrence of radial streaks called striations on the surface and difficulty in forming a film with a smooth surface. In addition, when forming a pattern on the coated film by the photolithography method, there is also a problem of residue generation in the unexposed portion.

[0005] An object of the present invention is to provide a photosensitive coloring composition for a color filter that can suppress the generation of striations, can form a film with a smooth surface, and can form a pattern that suppresses residues in unexposed portions.

Means for Solving the Problems

[0006] <1> A photosensitive coloring composition for a color filter containing a colorant (A), a resin (B), a polymerizable monomer (C), a photopolymerization initiator (D), and a solvent (E), The solvent (E) contains 0.5 to 15% by mass of a solvent (E1) satisfying the following (1) and (2) in 100% by mass of the photosensitive coloring composition, A photosensitive coloring composition for a color filter containing 15 to 80% by mass of a solvent (E2) satisfying the following (3) and (4) in 100% by mass of the photosensitive coloring composition. (1) The boiling point at atmospheric pressure (1013.25 hPa) is 180°C or higher and lower than 250°C (2) The vapor pressure at 20°C is 1 or higher and lower than 15 Pa (3) The boiling point at atmospheric pressure (1013.25 hPa) is 120°C or higher and lower than 150°C (4) The vapor pressure at 20°C is 400 or higher and lower than 1200 Pa <2> Furthermore, the photosensitive coloring composition for a color filter of <1> containing 0.5 to 15% by mass of a solvent (E3) satisfying the following (5) and (6) in 100% by mass of the photosensitive coloring composition. (5) The boiling point at atmospheric pressure (1013.25 hPa) is 150°C or higher and lower than 180°C (6) The vapor pressure at 20°C is 15 or higher and lower than 400 Pa <3> The photosensitive coloring composition for a color filter of <1> or <2>, wherein the solvent (E1) contains one or more solvents selected from the group consisting of diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol methyl ether, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol. A color filter having a filter segment formed from the photosensitive coloring composition for a color filter according to any one of <4><1> to <3>. A solid-state imaging device including the color filter of <5><4>. A liquid crystal display device including the color filter of <6><4>. An infrared sensor including the color filter of <7><4>.

Advantages of the Invention

[0007] According to the present invention described above, it is possible to provide a photosensitive coloring composition for a color filter that suppresses the generation of striations, can form a film with a smooth surface, and can form a pattern that suppresses residues in unexposed portions. Further, the present invention can provide a color filter, a solid-state imaging device, a liquid crystal display device, and an infrared sensor.

Brief Description of the Drawings

[0008]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0009] The terms used in this specification are defined. When expressed as “(meth)acryloyl,” “(meth)acrylic,” “(meth)acrylic acid,” “(meth)acrylate,” or “(meth)acrylamide,” unless otherwise specified, they represent “acryloyl and / or methacryloyl,” “acrylic and / or methacrylic,” “acrylic acid and / or methacrylic acid,” “acrylate and / or methacrylate,” or “acrylamide and / or methacrylamide,” respectively. “C.I.” mentioned in this specification means Color Index (C.I.). Colorants include pigments and dyes. 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 where the monomer forms a resin after polymerization. A monomer is a compound having a polymerizable unsaturated group. The polymerizable unsaturated group is an ethylenically unsaturated double bond such as a vinyl group, a (meth)acryloyl group, or a (meth)allyl group.

[0010] The photosensitive coloring composition of the present invention is a photosensitive coloring composition containing a colorant (A), a resin (B), a polymerizable monomer (C), a photopolymerization initiator (D), and a solvent (E), wherein the solvent (E) contains a solvent (E1) satisfying the following (1) and (2) and contains 0.5 to 15 parts by mass based on 100 parts by mass of the total amount of the photosensitive coloring composition, and contains a solvent (E2) satisfying the following (3) and (4) and contains 15 to 80 parts by mass based on 100 parts by mass of the total amount of the photosensitive coloring composition. (1) The boiling point at atmospheric pressure (1013.25 hPa) is 180°C or higher and lower than 250°C (2) The vapor pressure at 20°C is 1 or higher and lower than 15 Pa (3) The boiling point at atmospheric pressure (1013.25 hPa) is 120°C or higher and lower than 150°C (4) The vapor pressure at 20°C is 400 or higher and lower than 1200 Pa

[0011] The photosensitive coloring composition for a color filter contains 0.5 to 15 parts by mass of a solvent (E1) satisfying the above (1) and (2) with respect to 100 parts by mass of the total amount of the photosensitive coloring composition, and 15 to 80 parts by mass of a solvent (E2) satisfying the above (3) and (4) with respect to 100 parts by mass of the total amount of the photosensitive coloring composition, whereby the balance between the fluidity and the drying property of the film coated by the spin coating method can be optimized. Thereby, the generation of striations can be suppressed and a film with a smooth surface can be formed.

[0012] <Colorant (A)> The photosensitive coloring composition of the present invention contains a colorant (A). Examples of the colorant (A) include pigments and dyes. Pigments include organic pigments and inorganic pigments, and it is preferable to contain pigments in terms of resistance for color filter applications. Hereinafter, pigments classified as pigments in the Color Index are exemplified.

[0013] Red pigments include, for example, C.I. 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, 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, etc.

[0014] Orange pigments include, for example, C.I. Pigment Orange 36, 38, 43, 64, 71, 73, etc.

[0015] Yellow pigments include, for example, C.I. 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, 126, 127, 128, 129, 138, 139, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 185, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, etc.

[0016] Green pigments include, for example, C.I. 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.

[0017] Blue pigments include, for example, C.I. 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.

[0018] Violet pigments include, for example, C.I. 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, 50, etc.

[0019] Black pigments include, for example, C.I. Pigment Black 1, 6, 7, 12, 20, 31, etc.

[0020] In addition, examples of inorganic pigments include silica, talc, titanium oxide, zinc oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III) (red ocher), cadmium red, ultramarine, dark ultramarine, chromium oxide green, cobalt green, amber, synthetic iron black, and the like.

[0021] <Pigment derivative (b)> As the pigment derivative used as needed in the present invention, known pigment derivatives having an acidic group, a basic group, a neutral group, etc. in the organic dye residue can be used. For example, compounds having acidic substituents such as a sulfo group, a carboxy group, a phosphate group, and amine salts thereof, compounds having basic substituents such as a sulfonamide group and a tertiary amino group at the terminal, and compounds having neutral substituents such as a phenyl group and a phthalimidalkyl group can be mentioned. Since the resin-type dispersant used in combination has an acidic group, a pigment derivative having a basic group is preferred. Examples of the organic dye in the organic dye residue include diketopyrrolopyrrole-based pigments, anthraquinone-based pigments, quinacridone-based pigments, dioxazine-based pigments, perinone-based pigments, perylene-based pigments, thiazine indigo-based pigments, triazine-based pigments, benzimidazolone-based pigments, indole-based pigments such as benzisoindole, isoindoline-based pigments, isoindolinone-based pigments, quinophthalone-based pigments, naphthol-based pigments, fluorene-based pigments, metal complex-based pigments, azo-based pigments such as azo, disazo, and polyazo, and the like.

[0022] The pigment derivatives can be used alone or in a mixture of two or more.

[0023] The amount of the pigment derivative used is preferably 1 to 30 parts by mass, more preferably 3 to 25 parts by mass, and even more preferably 5 to 20 parts by mass with respect to 100 parts by mass of the pigment.

[0024] When a pigment derivative is added to the pigment and a refinement treatment such as acid pasting, acid slurry, dry milling, salt milling, or solvent salt milling is performed, the pigment derivative is adsorbed on the pigment surface, and the dispersed particle diameter of the pigment can be refined.

[0025] <Fine Particle Size of Pigment> The pigment is preferably used after being finely divided. The method of fine division is not particularly limited, and for example, any of wet grinding, dry grinding, and solution precipitation methods can be used. Among these, salt milling treatment by a kneader method, which is a type of wet grinding, is preferable. The average primary particle diameter determined by TEM (transmission electron microscope) of the finely divided pigment is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

[0026] For the salt milling treatment, a resin may be added as necessary. By adding a resin, the pigment is coated with the resin, and the stability, light resistance, etc. are improved. The type of the resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, it is preferably solid at room temperature, water-insoluble, and partially soluble in an organic solvent. The addition amount of the resin is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the pigment.

[0027] <Dye> Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, building dyes, sulfur dyes, etc. Further, derivatives of these dyes or lake pigments obtained by lake formation of the dyes can also be used.

[0028] The acid dye preferably has an acidic group such as a sulfonic acid or a carboxylic acid. The direct dye preferably forms a salt-forming compound with an inorganic salt of an acid dye or a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound. Further, a salt-forming compound that is a salt of an acid dye and a resin component having these functional groups is also preferable. Further, the salt-forming compound is easily obtained as a photosensitive coloring composition excellent in resistance (light resistance, solvent resistance) by sulfonamidation and modification into a sulfonic acid amide compound. Furthermore, a salt-forming compound of an acidic dye and a compound having an onium base is also preferable because it has excellent resistance (light resistance, solvent resistance). The compound having an onium base is preferably a resin having a cationic group.

[0029] Basic dyes can be used as they are, but salt-forming compounds formed by salt formation with organic acids, perchloric acid, or their metal salts are preferable. The salt-forming compounds of basic dyes are preferable because they have excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, for the salt-forming compounds of basic dyes, the anion component acting as a counterion is an organic sulfonic acid, organic sulfuric acid, fluorine group-containing phosphorus anion compound, fluorine group-containing boron anion compound, cyano group-containing nitrogen anion compound, an anion compound having a conjugate base of an organic acid having a halogenated hydrocarbon group, or a salt-forming compound formed by salt formation with an acidic dye. Note that the resistance is further improved when the salt-forming compound contains a polymerizable unsaturated group in the molecule.

[0030] The chemical structure of the dye includes, for example, azo dyes, disazo dyes, azomethine dyes (such as indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (such as benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, anthrapyridone dyes, etc.), carbonium dyes (such as diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinoneimine dyes (such as oxazine dyes, thiazine dyes, etc.), azine dyes, polymethine dyes (such as oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, etc. Among these, from the viewpoint of color characteristics such as hue, color separation property, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred.

[0031] The colorant (A) is preferably contained in an amount of 30 to 70% by mass in 100% by mass of the non-volatile content of the photosensitive coloring composition.

[0032] <Removal of metal> When a large amount of specific metal elements are present in the coloring composition as impurities other than the constituent components of the pigment, it inhibits the dispersion stability over time. Also, the heat resistance may decrease or the sensitivity may decrease. In addition, the color filter prepared using this may have the occurrence of foreign matters, and as a result, it is likely to cause a decrease in brightness. The total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) contained in the photosensitive coloring composition is preferably 500 ppm by mass or less.

[0033] The total amount of the specific metal elements is more preferably 300 mass ppm or less, and particularly preferably 200 mass ppm or less. The lower limit of the total amount of the specific metal elements is not particularly limited, but is preferably 1 mass ppm or more, and more preferably 5 mass ppm or more. Within the above range, a photosensitive coloring composition can be obtained that can suppress costs, has excellent storage stability, and forms a color filter with less generation of foreign matter and less decrease in lightness.

[0034] The amount of each specific metal element contained in the photosensitive coloring composition is preferably 100 mass ppm or less, and more preferably 50 mass ppm or less for each.

[0035] In addition, since metals such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co that constitute the pigment and impurities that do not constitute the pigment are to be suppressed, they can be removed in the same manner as the specific metal elements by, for example, the following methods. Furthermore, Mn, Cs, Ti, Co, Si, Pd, etc. may be mixed from materials (such as catalysts) used in the manufacturing process of various raw materials of the photosensitive coloring composition, so they should be removed as much as possible.

[0036] As methods for removing the pigment (A) or metals mixed in from the apparatus during the manufacturing process, there are methods such as washing with water according to JP-A-2010-83997, JP-A-2018-36521, JP-A-7-198928, JP-A-8-333521, JP-A-2009-7432, etc., and methods such as removing magnetic foreign matter with a magnet described in JP-A-2011-48736.

[0037] The content of the specific metal elements can be measured by inductively coupled plasma optical emission spectrometry (ICP).

[0038] <Resin (B)> The resin (B) in the present invention includes a resin-type dispersant (B1) and a binder resin (B2).

[0039] In the photosensitive coloring composition of the present invention, the content of the resin (B) is preferably 5 to 60 parts by mass, more preferably 10 to 50 parts by mass, based on the total mass of the colorant (A) (100 parts by mass).

[0040] <Resin type dispersant (B1)> The resin type dispersant (B1) preferably has an adsorption site that adsorbs to the colorant and a steric repulsion site that stably disperses the colorant particles. Examples of the resin type dispersant (B1) include an acidic resin type dispersant (B1-a), a basic resin type dispersant (B1-b), and other resin type dispersants. When classified by molecular structure, the resin type dispersant (B1) includes a comb-shaped structure resin, a chain block polymer, and a vinyl polymer having an aromatic carboxylic acid at the end.

[0041] <Acidic resin type dispersant (B1-a)> The acidic resin type dispersant (B1-a) is, for example, a comb-shaped dispersant having a main chain containing an aromatic carboxylic acid ester site having an ester bond formed by esterifying an aromatic compound having two or more acid anhydride groups and a compound having two or more hydroxyl groups, and a side chain containing a vinyl polymer site. The amount of the acid anhydride group used relative to 1 mol of the hydroxyl group is 0.9 to 1.5 mol, preferably 1.0 to 1.3 mol. In addition, the main chain containing the aromatic carboxylic acid ester site can have a blocking site derived from a monoalcohol. That is, a monoalcohol can be reacted with the acid anhydride group in the main chain to form an alcohol ester group and a carboxyl group. The photosensitive coloring composition containing a resin type dispersant having a blocking site has improved filterability and can suppress foreign substances on the coating film formed by coating. Furthermore, when the photosensitive coloring composition is coated, the re-dissolvability of the solid matter derived from the photosensitive coloring composition formed on a coating device such as a die coater in propylene glycol monomethyl ether acetate (hereinafter also referred to as PGMAc) is improved.

[0042] (Aromatic compound having two or more acid anhydride groups) Aromatic compounds having two or more acid anhydride groups include, for example, pyromellitic dianhydride, ethylene glycol dianhydride trimellitate, propylene glycol dianhydride trimellitate, butylene glycol dianhydride trimellitate, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenyl sulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyl diphenyl silane tetracarboxylic dianhydride, 3,3',4,4'-tetraphenyl silane tetracarboxylic dianhydride, 1,2,3,4-furan tetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy) diphenyl propane dianhydride, 3,3',4,4'-perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyl tetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenyl phthalic acid) dianhydride, m-phenylene-bis(triphenyl phthalic acid) dianhydride, bis(triphenyl phthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenyl phthalic acid)-4,4'-diphenyl methane dianhydride, 9,9-bis(3,4-dicarboxyphenyl) fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy) phenyl] fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride, etc. Among these, pyromellitic dianhydride, ethylene glycol dianhydride trimellitate, propylene glycol dianhydride trimellitate, and butylene glycol dianhydride trimellitate are preferred.

[0043] (Compound having two or more hydroxyl groups) As described above, the compound having two or more carboxyl groups preferably has a hydroxyl group and a thiol group in the molecule, and more preferably has two hydroxyl groups and one thiol group in the molecule.

[0044] Examples of the compound having two hydroxyl groups and one thiol group in the molecule include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerol), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, or 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0045] (Monoalcohol) Monoalcohols include, for example, monoalcohols such as methanol, ethanol, 1-butanol, 2-butanol, isobutanol, t-butanol, 1-pentanol, isopentyl alcohol, tert-pentyl alcohol, cyclopentanol, 1-hexanol, cyclohexanol, 1-heptanol, 1-octanol, 2-ethyl-1-hexanol, isononyl alcohol, 1-nonyl alcohol, amyl alcohol, lauryl alcohol, n-butyl alcohol, isobutyl alcohol, cyclohexanol, benzyl alcohol, methylcyclohexanol, etc., monoalcohols having an ether group such as 3-methoxy-3-methyl-1-butanol, 3-methoxybutanol, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monobutyl ether, diethylene glycol monomethyl ether, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol monophenyl ether, propylene glycol monoethyl ether, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether. Examples include monoalcohols having a carbonyl group such as methyl lactate, ethyl lactate, diacetone alcohol, etc.

[0046] The monoalcohol is preferably a compound having an ether group or a carbonyl group. By having an ether group or a carbonyl group at the end of the main chain of the dispersant, the redissolubility of the dispersant in PGMAc is improved. Among these, 3-methoxybutanol, propylene glycol monomethyl ether, and diacetone alcohol are preferred.

[0047] The main chain, which is an aromatic carboxylic acid ester moiety, may have a blocking site reacted with water in addition to the blocking site derived from the monoalcohol.

[0048] Regarding the synthesis of the blocking site, the amount of monoalcohol used with respect to the acid anhydride group is preferably 1 to 30 molar equivalents, more preferably 1.5 to 20 molar equivalents, per 1 equivalent of the acid anhydride group remaining in the main chain. When it is 1 molar equivalent or more, no acid anhydride group remains and the storage stability is good. When it is 30 molar equivalents or less, the transesterification reaction due to the ester bond between the monoalcohol and the dispersant hardly occurs, and the decrease in molecular weight hardly occurs.

[0049] (Side chain based on the vinyl polymer moiety) The side chain based on the vinyl polymer moiety is formed by the polymerization of a monomer. The polymerization is preferably carried out in the presence of a compound having two hydroxyl groups and one thiol group in the molecule. A vinyl polymer having a hydroxyl group near the end is formed by the polymerization. There are two methods for the synthesis of the acidic resin type dispersant (B1-a). The first is a method of synthesizing the main chain after the synthesis of the vinyl polymer. The second is a method of synthesizing the main chain using a compound having two hydroxyl groups and one thiol group in the molecule, and then forming the vinyl polymer moiety starting from the thiol group of the main chain.

[0050] For the synthesis of the vinyl polymer, for example, the following monomers can be used. For example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylate of methylolated melamine, various acrylate esters and methacrylate esters such as epoxy (meth)acrylate and urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, etc. can be mentioned.

[0051] (Basic resin type dispersant (B1-b)) The basic resin type dispersant (B1-b) includes, for example, a nitrogen atom-containing graft copolymer, a nitrogen atom-containing acrylic block copolymer having a functional group selected from a tertiary amino group, a quaternary ammonium base, and a nitrogen-containing heterocyclic ring in the side chain, and a urethane-based polymer dispersant, etc.

[0052] Other resin type dispersants include, for example, urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamidates, hydroxyl group-containing polycarboxylic acid esters, and modified products thereof, oil-based dispersants such as amides and salts thereof formed by the reaction of poly(lower alkyleneimine) and a polyester having a free carboxyl group, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylate copolymers, styrene-maleic acid copolymers, water-soluble resins and water-soluble polymer compounds such as polyvinyl alcohol and polyvinylpyrrolidone, polyester-based, modified polyacrylate-based, ethylene oxide / propylene oxide adduct compounds, phosphate ester-based, etc.

[0053] The resin type dispersant (B1) can be used alone or in combination of two or more.

[0054] The content of the resin type dispersant (B1) is preferably 3 to 200% by mass, more preferably 5 to 100% by mass with respect to 100 parts by mass of the colorant (A). When contained in an appropriate amount, the film-forming property is improved.

[0055] <Binder resin (B2)> The binder resin (B2) is a resin with a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm when forming a film with a thickness of 2 μm. In addition, a transmittance of 95% or more is preferable. From the perspective of curability, the binder resin includes, for example, thermoplastic resins, active energy ray curable resins, etc. The active energy ray curable resin is a resin obtained by imparting a polymerizable unsaturated group to a thermoplastic resin. Also, from the perspective of physical properties, an alkali-soluble resin is preferable for the binder resin. Alkali solubility is for imparting developability solubility in the alkali development process during the production of the color filter, and an acidic group is required. The binder resin (B2) is preferably a chain random polymer. The chain includes branched chains.

[0056] <Thermoplastic resin> Examples of the thermoplastic resin include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resins.

[0057] <Alkali-soluble resin> The alkali-soluble resin can be classified into an alkali-soluble resin (B2-1) having no active energy ray reactive group (hereinafter referred to as the alkali-soluble resin (B2-1)) and an alkali-soluble resin (B2-2) having an active energy ray reactive group (hereinafter referred to as the alkali-soluble resin (B2-2)).

[0058] <Alkali-soluble resin (B2-1)> The alkali-soluble resin (B2-1) includes, for example, resins having acidic groups such as carboxyl groups and sulfone groups. Thermoplastic resins having alkali solubility include, for example, acrylic resins having acidic groups, α-olefin / (anhydrous) maleic acid copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (anhydrous) maleic acid copolymers. Among these, acrylic resins having acidic groups and styrene / styrene sulfonic acid copolymers are preferable in terms of improving developability, heat resistance, and transparency.

[0059] <Alkali-soluble resin (B2-2)> The alkali-soluble resin (B2-2) is not particularly limited as long as it is a resin having a polymerizable unsaturated group. For example, resins synthesized by the following methods (i) and (ii) are preferable. This improves the crosslinking density of the film formed from the photosensitive coloring composition by light irradiation.

[0060] [Method (i)] Method (i) includes, for example, first synthesizing a polymer of an epoxy group-containing monomer and other monomers. Next, a carboxyl group-containing monomer is added to the epoxy group of the polymer, and a polybasic acid anhydride is reacted with the generated hydroxyl group to obtain an alkali-soluble resin (C2).

[0061] Examples of the epoxy group-containing monomer include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. Among these, glycidyl (meth)acrylate is preferable from the viewpoint of reactivity.

[0062] Examples of the monocarboxyl group-containing monomer include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted products of (meth)acrylic acid.

[0063] Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like.

[0064] The monomer and the polybasic acid anhydride can each be used alone or in combination of two or more.

[0065] Also, as a method similar to method (i), for example, a carboxyl group-containing monomer and other monomers are synthesized to prepare a polymer. Then, an epoxy group-containing monomer is added to a part of the carboxyl groups of the polymer to obtain an alkali-soluble resin (C2).

[0066] [Method (ii)] Method (ii) is, for example, a method in which a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers are synthesized to prepare a polymer. Then, the isocyanate group of an isocyanate group-containing monomer is reacted with the hydroxyl groups of the polymer.

[0067] As the hydroxyl group-containing monomer, the monomers already exemplified can be used. Among them, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferable in terms of being less likely to generate foreign substances in the film. Also, glycerol mono(meth)acrylate is preferable in terms of photosensitivity.

[0068] Examples of the monomer having an isocyanate group include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0069] As the other monomers, for example, the monomers exemplified in the synthesis of the above vinyl polymer and the following monomers can be used. Examples include EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of parachloromylphenol, EO-modified (meth)acrylate of nonylphenol, PO-modified (meth)acrylate of nonylphenol, and the like.

[0070] The acid value of the alkali-soluble resin is preferably 50 to 200 mgKOH / g, more preferably 70 to 180 mgKOH / g, and even more preferably 90 to 170 mgKOH / g in order to impart alkali developability solubility.

[0071] The weight average molecular weight (Mw) of the binder resin is preferably 2,000 or more and 40,000 or less, more preferably 3,000 or more and 30,000 or less, and even more preferably 4,000 or more and 20,000 or less. Also, the value of Mw / Mn (number average molecular weight) is preferably 10 or less. When the weight average molecular weight (Mw) is 2,000 or more, the adhesion to the substrate is improved and a good pattern is easily obtained. When it is 40,000 or less, the alkali developability solubility is improved and residues are less likely to occur.

[0072] The content of the binder resin is preferably 1 to 60% by mass, more preferably 2 to 40 parts by mass in 100% by mass of the non-volatile content of the photosensitive coloring composition. When blended in an appropriate amount, the adhesion between the film and the substrate is further improved.

[0073] Each raw material used for the synthesis of the binder resin (B2) can be used alone or in combination of two or more.

[0074] The binder resin (B2) can be used alone or in combination of two or more.

[0075] <Polymerizable compound (C)> The polymerizable compound (C) is a monomer or oligomer having a polymerizable unsaturated group. Examples of the polymerizable compound (C) include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanuric acid EO-modified di(meth)acrylate, isocyanuric acid EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, (meth)acrylate of methylolated melamine, epoxy (meth)acrylate, urethane acrylate and other various acrylate esters and methacrylate esters, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile and the like. Among these, it is preferable to contain a polymerizable compound (C1) having one or more alkylene oxide chains (hereinafter referred to as AO chains), which exerts an effect on the surface smoothness of the coating film, which is an object of the present invention.

[0076] Polymerizable compound (C1) having one or more alkylene oxide chains The polymerizable compound (C1) having one or more alkylene oxide chains includes, for example, the polymerizable compounds shown in the following (C1-1) and (C1-2), and the polymerizable compounds of (C1-3) to (C1-6).

[0077]

Chemical formula

[0078]

Chemical formula

[0079] JPEG2025077109000004.jpg54149

[0080] In the above general formula, n is an integer from 0 to 14 (provided that not all n are 0), m is an integer from 1 to 8, and R and T may be different from each other.

[0081] As the polymerizable compound (C1) having one or more alkylene oxide chains, the following compounds are more preferable.

Chemical formula

Chemical formula

Chemical formula

[0082] The polymerizable compound (C) can be used alone or in combination of two or more.

[0083] The content of the overlapping compound (C) is preferably 1 to 50% by mass, more preferably 2 to 40 parts by mass, in 100% by mass of the non-volatile content of the photosensitive coloring composition. When blended in an appropriate amount, the curability and developability are further improved.

[0084] [Photoinitiator (D)] As for the photoinitiator (D), various initiators can be used, and an oxime ester-based photoinitiator (D1) is preferred.

[0085] (Oxime ester-based photoinitiator) The oxime ester-based photoinitiator absorbs ultraviolet rays, causing the cleavage of the N-O bond of the oxime and generating iminyl radicals and alkoxy radicals. These radicals further decompose to generate highly active radicals. Therefore, compared with the case of using other photoinitiators, a pattern can be formed with a smaller exposure amount, improving the photocurability.

[0086] Examples of the oxime ester-based photoinitiator include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentan-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-(4-toluenesulfonyloxy)iminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one. Commercially available products of oxime compounds include IRGACURE-OXE01, IRGACURE-OXE02, IRGACURE-OXE03, IRGACURE-OXE04 (manufactured by BASF Japan Ltd.), TR-PBG-304, TR-PBG-305, TR-PBG-3057, TR-PBG-345, TR-PBG-358 (manufactured by Changzhou Qiangli Electronic New Materials Co., Ltd.), Adeka Optomer N-1919, Adeka Arcles NCI-730, NCI-831, NCI-930 (manufactured by ADEKA).

[0087] When classifying oxime ester-based photoinitiators by their skeletons, there are the carbazole skeleton, the fluorene skeleton, the diphenyl skeleton, and the dioxime type having two oxime ester groups. Also, specific structures contained in the compound are preferably, for example, a hydroxyl group, a nitro group, a carbonyl group, a fluorinated carbon group, and benzofuran.

[0088] (Oxime ester-based photoinitiator (D1-1) having a diphenyl skeleton) The oxime ester-based photoinitiator having a diphenyl skeleton is exemplified below. [Chemical formula]

[0089] Among these, the compound of (D1-1-6) is more preferable because of the good balance of sensitivity and the heat resistance and solvent resistance after curing of the photosensitive coloring composition.

[0090] (Oxime ester-based photoinitiator (D1-2) having a carbazole skeleton) The oxime ester-based photoinitiator having a carbazole skeleton is exemplified below. Compounds having two oxime ester groups are exemplified separately. [Chemical formula] JPEG2025077109000010.jpg103147JPEG2025077109000011.jpg103142

[0091] Among these, the compounds of (D1-2-3) to (D1-2-14) are more preferable because of the good balance of sensitivity and the heat resistance and solvent resistance after curing.

[0092] (Oxime ester-based photoinitiator (D1-3) having a fluorene skeleton) The oxime ester-based photoinitiator having a fluorene skeleton is exemplified below. [Chemical formula]

[0093] Among these, the compounds of (D1-3-1) to (D1-3-3) are more preferable because of the good balance of sensitivity, heat resistance and solvent resistance after curing of the photosensitive coloring composition.

[0094] (Photopolymerization initiator having two oxime ester groups) Photopolymerization initiators having two oxime ester groups on both sides of a carbazole skeleton or a phenothiazine skeleton are exemplified below.

Chemical formula

[0095] Among these, the compound of (D1-4-1) is more preferable because of the good balance of sensitivity, heat resistance and solvent resistance after curing of the photosensitive coloring composition.

[0096] Other photoinitiators other than oxime ester-based photoinitiators include, for example, acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; benzoin-based compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone-based compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone-based compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; triazine-based compounds such as 2,4,6-trichloros-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-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine;Phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; titanocene compounds; or oxime ester compounds, etc. can be mentioned.;

[0097] The photoinitiator (D) can be used alone or in combination of two or more kinds.;

[0098] The content of the photoinitiator (D) is preferably 1 to 100 parts by mass, more preferably 5 to 50 parts by mass, and still more preferably 15 to 30 parts by mass with respect to 100 parts by mass of the polymerizable compound (C). When used in an appropriate amount, photocurability without excess or deficiency can be obtained.;

[0099] <Sensitizer> The photosensitive coloring composition can further contain a sensitizer.; Examples of the sensitizer include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. Examples of the sensitizer 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, 3,6-dibenzoyl-N-ethylcarbazole, etc.;

[0100] The sensitizer can be used alone or in combination of two or more kinds.;

[0101] The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the photoinitiator. When contained in an appropriate amount, the curability and developability are further improved.;

[0102] <Thiol-based chain transfer agent> The photosensitive coloring composition can contain a chain transfer agent. As the chain transfer agent, a thiol-based chain transfer agent is preferable. When the thiol-based chain transfer agent is used in combination with a photoinitiator, during radical polymerization after light irradiation, thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated, and the sensitivity of the photosensitive coloring composition is improved.

[0103] As the thiol-based chain transfer agent, a polyfunctional thiol having two or more thiol groups (SH groups) is preferable. More preferably, the thiol-based chain transfer agent has four or more SH groups. As the number of functional groups increases, it becomes easier to photocure from the surface to the deepest part of the film.

[0104] Examples of the polyfunctional thiol include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristthioglycolate, trimethylolpropane tristthiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris(2-hydroxyethyl) isocyanurate trimercaptopropionate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine, etc. Preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristthiopropionate, and pentaerythritol tetrakisthiopropionate are mentioned.

[0105] The thiol-based chain transfer agent can be used alone or in combination of two or more.

[0106] The content of the thiol-based chain transfer agent is preferably 0.1 to 10% by mass, more preferably 0.1 to 3% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When contained in an appropriate amount, the photosensitivity and the taper shape are improved, and wrinkles are less likely to occur on the film surface.

[0107] <Polymerization inhibitor> The photosensitive coloring composition can contain a polymerization inhibitor. This can suppress the photosensitivity due to the diffracted light of the mask during the exposure of the photolithography method, making it easier to obtain a pattern with a desired shape.

[0108] Examples of the polymerization inhibitor include alkylcatechol-based compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol; alkylresorcinol-based compounds such as 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol; alkylhydroquinone-based compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2,5-di-tert-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide, triphenylphosphine oxide; phosphite compounds such as triphenylphosphite, trisnonylphenylphosphite; pyrogallol, phloroglucin, and the like.

[0109] The content of the polymerization inhibitor is preferably 0.01 to 0.4 parts by mass in 100 parts by mass of the non-volatile content of the photosensitive coloring composition. When contained in an appropriate amount, a good pattern shape is easily obtained.

[0110] <Ultraviolet absorber> The photosensitive coloring composition can contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate compounds. The ultraviolet absorber may be an oligomer or a polymer.

[0111] 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, a mixture of 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, C7-9 side chain and linear alkyl ester, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, the reaction product of methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300, 2-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol], 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl 3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0112] 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-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester, 2,4-bis[2-hydroxy-4-butoxyphenyl]-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, and the like.

[0113] Benzophenone compounds include, for example, 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octadecyloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, and the like.

[0114] Salicylic acid ester compounds include, for example, phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like.

[0115] The content of the ultraviolet absorber is preferably 0.01 to 1 part by mass in 100 parts by mass of the nonvolatile components of the photosensitive coloring composition.

[0116] <Antioxidant> The photosensitive coloring composition of the present invention can contain an antioxidant. The antioxidant can prevent the photoinitiator and thermosetting compound contained in the photosensitive coloring composition from being oxidized and yellowed by the heat treatment during thermosetting or ITO annealing, thereby improving the transmittance of the coating film. In particular, when the concentration of the colorant in the coloring composition is high, the amount of the crosslinking component in the coating film decreases, so a phenomenon of stronger yellowing in the heat treatment is observed due to measures such as using a highly sensitive crosslinking component or increasing the amount of the photoinitiator. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a coating film with a high transmittance can be obtained.

[0117] Examples of the antioxidant include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In this specification, the antioxidant is preferably a compound that does not contain a halogen atom.

[0118] Among these, from the viewpoint of achieving both the transmittance and sensitivity of the coating film, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0119] The antioxidant can be used alone or in combination of two or more.

[0120] The content of the antioxidant is preferably 0.5 to 5.0% by mass in 100% by mass of the non-volatile content of the photosensitive coloring composition. When contained in an appropriate amount, the transmittance, spectral characteristics, and sensitivity are improved.

[0121] <Levelling agent> The photosensitive coloring composition can contain a levelling agent. Thereby, the coatability of the composition and the drying property of the film are improved. Examples of the levelling agent include silicone-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and the like.

[0122] Examples of silicone surfactants include linear polymers composed of siloxane bonds and modified siloxane polymers with organic groups introduced into the side chains or terminals.

[0123] Examples of commercially available silicone surfactants include BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345 / 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, 3570 manufactured by BYK Chemie; FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Toray Dow Corning; 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 manufactured by Shin-Etsu Chemical Co., Ltd.

[0124] Examples of fluorosurfactants include surfactants having fluorocarbon chains.

[0125] Examples of commercially available fluorosurfactants include Surflon S-242, S-243, S-420, S-611, S-651, S-386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, F-477, F-551, F-552, F-555, F-558, F-560, F-570, F-575, F-576, R-40-LM, R-41, RS-72-K, DS-21 manufactured by DIC Corporation; FC-4430, FC-4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; Ftergent 602A manufactured by Neos Co., Ltd.

[0126] Surfactants can be used alone or in combination of two or more.

[0127] The content of the surfactant is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, in 100% by mass of the non-volatile content of the photosensitive coloring composition. When contained in an appropriate amount, the coating property, pattern adhesion, and transmittance are improved in a well-balanced manner.

[0128] <Storage stabilizer> The photosensitive coloring composition can contain a storage stabilizer to stabilize the viscosity of the composition over time. Examples of the storage stabilizer include quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine, and phosphites.

[0129] The content of the storage stabilizer is preferably 0.1 to 10% by mass with respect to 100 parts by mass of the colorant (A).

[0130] <Adhesion improver> The photosensitive coloring composition can contain an adhesion improver. Examples of the adhesion improver include silane coupling agents. Silane coupling agents include, for example, vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane; (meth)acrylic silanes such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane; aminosilanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercaptos such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureidos such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; isocyanates such as 3-isocyanatopropyltriethoxysilane.

[0131] The content of the adhesion improver is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass, based on 100 parts by mass of the colorant (A). When contained in an appropriate amount, the photosensitivity of the photosensitive coloring composition is improved, the adhesion of the film is further improved, and the resolution of the pattern is also further improved.

[0132] <Solvent (E)> The photosensitive coloring composition contains a solvent (E). This makes it easy to adjust the viscosity of the photosensitive coloring composition, so that a film with a smooth surface is easily formed. The solvent may be appropriately selected according to the purpose of use and contained in an appropriate amount.

[0133] The solvent (E) contains 0.5 to 15% by mass of a solvent (E1) satisfying the following (1) and (2) in 100% by mass of the photosensitive coloring composition, and contains 15 to 80% by mass of a solvent (E2) satisfying the following (3) and (4) in 100% by mass of the photosensitive coloring composition (1) The boiling point at atmospheric pressure (1013.25 hPa) is 180°C or higher and lower than 250°C (2) The vapor pressure at 20°C is 1 Pa or higher and lower than 15 Pa (3) The boiling point at atmospheric pressure (1013.25 hPa) is 120°C When an appropriate amount of the solvent (E1) and the solvent (E2) are contained, the balance between the coatability and the drying property of the photosensitive coloring composition is improved at a high level. In addition, the content of the solvent (E1) is preferably 3 to 10% by mass. The content of the solvent (E2) is preferably 50 to 80% by mass.

[0134] The solvent (E) further contains a solvent (E3) satisfying the following (5) and (6) and more preferably contains 0.5 to 15 parts by mass with respect to 100 parts by mass of the total amount of the photosensitive coloring composition. (5) The boiling point at atmospheric pressure (1013.25 hPa) is 150°C or higher and lower than 180°C (6) The vapor pressure at 20°C is 15 Pa or higher and lower than 400 Pa In addition, the content of the solvent (E3) is preferably 4 to 12% by mass.

[0135] When the photosensitive coloring composition for a color filter further contains an appropriate amount of the solvent (E3) satisfying the above (5) and (6), the balance between the fluidity and the drying property of the film can be highly optimized.

[0136] <Solvent (E1)> The solvent (E1) includes, for example, diethylene glycol (boiling point 245 °C / vapor pressure 2.7 Pa), diethylene glycol monoethyl ether (boiling point 202 °C / vapor pressure 13 Pa), diethylene glycol monobutyl ether (boiling point 231 °C / vapor pressure 3 Pa), dipropylene glycol monobutyl ether (boiling point 229 °C / vapor pressure 8 Pa), tripropylene glycol methyl ether (boiling point 243 °C / vapor pressure 3 Pa), 1,2-butanediol (boiling point 193 °C / vapor pressure 2.7 Pa), 1,3-butanediol (boiling point 207 °C / vapor pressure 8 Pa), 1,4-butanediol (boiling point 228 °C / vapor pressure less than 1 Pa). Among these, diethylene glycol monoethyl ether (boiling point 202 °C / vapor pressure 5.3 Pa) and 1,2-butanediol (boiling point 193 °C / vapor pressure 2.7 Pa) are preferred in terms of suppressing the occurrence of striations and forming a smoother surface film.

[0137] <Solvent (E2)> The solvent (E2) includes, for example, propylene glycol monomethyl ether acetate (boiling point 146 °C / vapor pressure 490 Pa), propylene glycol monomethyl ether (boiling point 120 °C / vapor pressure 1200 Pa), cyclopentanone (boiling point 131 °C / vapor pressure 1150 Pa). Among these, propylene glycol monomethyl ether acetate is preferred.

[0138] <Solvent (E3)> Examples of the solvent (E3) include 3-methoxybutanol (boiling point 161 °C / vapor pressure 17 Pa), 1-butoxy-2-propanol (boiling point 170 °C / vapor pressure 139 Pa), ethylene glycol mononormal butyl ether (boiling point 171 °C / vapor pressure 117 Pa), and ethyl 3-ethoxypropionate (boiling point 166 °C / vapor pressure 200 Pa).

[0139] (Other solvent (E4)) The solvent (E) can contain other solvents (E4) other than the above. Other solvents (E4) include, for example, methyl 3-methoxypropionate (boiling point 142 °C / vapor pressure 240 Pa), 2-ethyl-1-hexanol (boiling point 185 °C / vapor pressure 48 Pa), 1-butanol (boiling point 118 °C / vapor pressure 580 Pa), 1,3-butylene glycol diacetate (boiling point 232 °C / vapor pressure 17 Pa), propylene glycol diacetate (boiling point 190 °C / vapor pressure 30 Pa), dipropylene glycol methyl normal propyl ether (boiling point 203 °C / vapor pressure 80 Pa), and the like.

[0140] <Method for producing a photosensitive composition> The photosensitive colored composition can be prepared, for example, by performing a dispersion treatment using a colorant (A), a resin-type dispersant (B1), a solvent, etc. to produce a pigment dispersion. Then, the pigment dispersion, a binder resin (B2), a polymerizable monomer (C), and a photopolymerization initiator (D) are mixed. The timing of blending each material is arbitrary. Also, the dispersion step can be performed multiple times. The resin-type dispersant (B1) or the binder resin (B2) may include any one or more of them.

[0141] For the above dispersion treatment, for example, a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor and other dispersion devices can be used.

[0142] <Removal of coarse particles> The photosensitive colored composition of the present invention is preferably subjected to removal of coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and mixed dust by means such as centrifugal separation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or a membrane filter. Thus, the colored composition preferably does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

[0143] <Amount of moisture in the photosensitive colored composition> In the photosensitive coloring composition of the present invention, the water content contained in the photosensitive coloring composition is preferably 2% by mass or less. When the water content is as described above, the photosensitive coloring composition is excellent in dispersion stability even after storage over time and the sensitivity does not decrease.

[0144] In addition, the water content contained in the photosensitive coloring composition is preferably 1.8% by mass or less, and more preferably 1.6% by mass or less.

[0145] Examples of the method for controlling the water content include, for example, a method of producing the photosensitive coloring composition while blowing dry inert gas, a method of charging molecular sieves after production for dehydration, and the like. Among these, the former method is preferred.

[0146] The water content can be measured by a known method such as the Karl Fischer method.

[0147] <Amount of toluene in the photosensitive coloring composition> The photosensitive coloring composition of the present invention can contain toluene. The toluene content is preferably 0.1 to 10 ppm by mass in the photosensitive coloring composition. The upper limit of the toluene content is preferably 9 ppm by mass or less, more preferably 8 ppm by mass or less, and still more preferably 7 ppm by mass or less. The lower limit is preferably 0.2 ppm by mass or more, more preferably 0.3 ppm by mass or more, and still more preferably 0.4 ppm by mass or more.

[0148] <Substrate, coating method, and pattern formation> Examples of the substrate include substrates made of materials such as glass, resin, and silicon. An organic light-emitting layer may be formed on these substrates. In addition, an imaging element such as a CCD or CMOS may be formed on the substrate. Further, a primer layer may be provided on the substrate as necessary for improving adhesion to an upper layer, preventing diffusion of substances, and planarizing the substrate surface.

[0149] Known coating methods can be used. For example, the dropping method, slit coating method, spray method, roll coating method, spin coating method, casting coating method, inkjet method, flexographic printing, screen printing, gravure printing, offset printing, etc. can be mentioned.

[0150] The thickness of the film can be appropriately adjusted according to the purpose. The thickness of the film is preferably 0.05 - 20.0 μm, and more preferably 0.3 - 10.0 μm.

[0151] Next, a pattern is formed. Examples of the method for forming a pattern include the photolithography method and the dry etching method. When used as a flat film, the step of forming a pattern may not be performed, and after coating, it is dried as necessary.

[0152] Hereinafter, the method for forming a pattern will be described in detail.

[0153] 〔Exposure step〕 In the exposure step, the colored layer is exposed to a specific pattern through a mask using an exposure apparatus such as a stepper. Thereby, a cured film is obtained. For exposure, ultraviolet rays such as ArF light, KrF light, g - ray, h - ray, i - ray, etc. are preferably used.

[0154] 〔Development step〕 Next, by performing an alkali development treatment, the layer of the unexposed portion is eluted into an aqueous alkali solution, and only the cured portion remains to obtain a patterned film. Examples of the alkali developer 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, 1,8 - diazabicyclo - [5.4.0] - 7 - undecene, etc. The concentration of the alkaline developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, roughness and peeling of the pattern are suppressed, and the residual film rate after development is improved. Examples of the development method include a dip method, a spray method, a paddle method, etc. The development temperature is preferably 15 to 40°C. After alkaline development, it is preferable to wash with pure water.

[0155] 〔Post-baking process〕 After development, heat treatment (post-baking) can be performed as necessary. The post-baking improves the resistance of the film. The temperature is preferably 80 to 300°C. Also, the time is preferably about 2 minutes to 1 hour. When a material with low heat resistance is used for the substrate, or when an organic electroluminescence element is used as the light source, the temperature is preferably 150°C or lower, more preferably 130°C or lower.

[0156] <Optical filter> The film of the present invention can be used for an optical filter. The optical filter can be used, for example, as a color filter which is a component of a liquid crystal display device, a solid-state imaging device, an organic EL display device, etc., an infrared cut filter which is a component of an infrared sensor, etc., an infrared transmission filter, etc. <Color filter> The color filter of the present invention preferably has filter segments formed by a photosensitive coloring composition. The color filter of the present invention can include, for example, a red filter segment, a green filter segment, and a blue filter segment. Also, the color filter can have a magenta filter segment, a cyan filter segment, a yellow filter segment, etc. instead of or together with these.

[0157] <Method for manufacturing a color filter> It is preferable that the color filter first forms a black matrix on a substrate and then forms filter segments. Note that a thin-film transistor (TFT) can be formed on the substrate in advance and then the black matrix can be formed. Examples of the black matrix include inorganic films such as chromium, multi-layer films of chromium / chromium oxide, titanium nitride, and resin films in which a light-shielding agent is dispersed.

[0158] In this specification, the color filter can be used for applications such as solid-state imaging devices, infrared sensors, organic EL display devices, quantum dot display devices, electronic paper, and head-mounted displays, in addition to liquid crystal display devices.

[0159] <Liquid crystal display device> As an example of an image display device, a liquid crystal display device will be described. The liquid crystal display device of the present invention includes a color filter. The liquid crystal display device includes the color filter of the present invention and a light source. Examples of the light source include a cold cathode tube (CCFL) and a white LED. In the present invention, it is preferable to use a white LED in terms of expanding the red reproduction region. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 including the color filter of the present invention. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 disposed opposite to each other with a gap therebetween, and liquid crystal LC is encapsulated therebetween.

[0160] On the inner surface of the first transparent substrate 11, a TFT (thin-film transistor) array 12 is formed, and on it, a transparent electrode layer 13 made of, for example, ITO is formed. An alignment layer 14 is provided on the transparent electrode layer 13. Also, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0161] On the other hand, on the inner surface of the second transparent substrate 21, the color filter 22 of the present invention is formed. The red, green, and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0162] The color filter 22 is covered, and a transparent protective film (not shown) is formed as necessary. Further, a transparent electrode layer 23 made of, for example, ITO is formed thereon, and an alignment layer 24 is provided to cover the transparent electrode layer 23.

[0163] Also, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

[0164] The liquid crystal LC is aligned according to driving modes such as TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In - Plane Switching), VA (Vertical Alignment), and OCB (Optically Compensated Birefringence). On the inner surface of the first transparent substrate 11, a TFT (Thin Film Transistor) array 12 is formed, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. Also, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0165] On the other hand, the color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. The red, green, and blue filter segments constituting the color filter 22 are separated by a black matrix (not shown).

[0166] The color filter 22 is covered, and a transparent protective film (not shown) is formed as necessary. Further, a transparent electrode layer 23 made of, for example, ITO is formed thereon, and an alignment layer 24 is provided to cover the transparent electrode layer 23.

[0167] Also, a polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Note that a backlight unit 30 is provided below the polarizing plate 15.

[0168] The white LED light source includes those formed by forming a fluorescent filter on the surface of a blue LED and those containing a phosphor in the resin package of a blue LED. It has a wavelength (λ3) at which the emission intensity is maximum within the range of 430 nm to 485 nm, a wavelength (λ4) at which the emission intensity is maximum within the range of 530 nm to 580 nm, and a wavelength (λ5) at which the emission intensity is maximum within the range of 600 nm to 650 nm. Also, the ratio (I4 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio (I5 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less. A white LED light source (LED1) having such spectral characteristics, or a white LED light source (LED2) having a wavelength (λ1) at which the emission intensity is maximum within the range of 430 nm to 485 nm, a peak wavelength (λ2) of the second emission intensity within the range of 530 nm to 580 nm, and the ratio (I2 / I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 being 0.2 or more and 0.7 or less is preferred.

[0169] Specific examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.).

[0170] Specific examples of LED2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D (manufactured by Nichia Chemical Industries, Ltd.).

[0171] <Solid-state imaging device> The solid-state imaging device of the present invention includes a color filter. Examples of the form in which the color filter is used in the solid-state imaging device include a form in which a plurality of photodiodes constituting the light-receiving area of the solid-state imaging device (CCD image sensor, CMOS image sensor, or organic CMOS image sensor, etc.) and a light-receiving element made of polysilicon or the like are provided on a substrate, and the cured film of the present invention is provided on the light-receiving element formation surface side or the side opposite to the formation surface.

[0172] <Infrared sensor> The solid-state imaging device of the present invention includes a color filter. The form used for the infrared sensor is not particularly limited. FIG. 2 is a schematic cross-sectional view showing a configuration example of an infrared sensor including the film of the present invention. The infrared sensor shown in FIG. 2 includes 100 and a solid-state imaging device 110.

[0173] The imaging region provided on the solid-state imaging device 110 is configured by combining an infrared cut filter 111 and a color filter 112.

[0174] The infrared cut filter 111 can be formed using the resin composition of the present invention, transmits light in the visible light region (for example, light with a wavelength of 400 to 700 nm), and shields light in the infrared region.

[0175] The color filter 112 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed. For example, a color filter in which pixels of red (R), green (G), and blue (B) are formed is used.

[0176] Between the infrared transmission filter 113 and the solid-state imaging device 110, a resin film 114 that can transmit light having a wavelength transmitted through the infrared transmission filter 113 is disposed. The infrared transmission filter 113 is a filter that shields light in the visible light region and transmits infrared light of a specific wavelength, and can be formed using the resin composition of the present invention.

[0177] On the incident light h side of the color filter 112 and the infrared transmission filter 113, a microlens 115 is disposed. A planarization film 116 is formed so as to cover the microlens 115.

[0178] In the form shown in FIG. 2, the resin film 114 is disposed, but an infrared transmission filter 113 may be formed instead of the resin film 114.

[0179] According to this infrared sensor, since image information can be captured simultaneously, motion sensing or the like that recognizes an object to be detected for motion is possible. Also, according to this infrared sensor, since distance information can be obtained, photographing an image including 3D information or the like is also possible. Furthermore, this infrared sensor can also be used as a biometric sensor.

[0180] Also, the color filter of the present invention can also be used in applications such as quantum dot displays.

Example

[0181] Hereinafter, the present invention will be described by way of examples. However, the present invention is not limited to the examples. In the examples, "parts" represents "parts by mass" and "%" represents "% by mass".

[0182] Prior to the examples, the calculation methods for measuring the average molecular weight of the resin and the acid value of the resin will be described.

[0183] <Average primary particle diameter of pigment> The average primary particle diameter of the pigment was measured by a general method of directly measuring the size of the primary particles from a transmission electron microscope (TEM) photograph. Specifically, the minor axis diameter and the major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle diameter of the pigment particles. Next, for 100 or more pigment particles, the volume (weight) of each particle was approximated by a rectangular parallelepiped with the obtained particle diameter, and the volume average particle diameter was taken as the average primary particle diameter.

[0184] (Measurement of dispersed particle diameter) Using the Microtrac UPA-EX150 of Nikkiso Co., Ltd. that employs the dynamic light scattering method (FFT power spectrum method), the particle permeability was set to the absorption mode, the particle shape was set to non-spherical, and D50 was set as the average diameter. The dilution solvents for measurement were respectively the solvents used for the dispersion, and the samples treated with ultrasonic waves were measured immediately after sample preparation.

[0185] (Average molecular weight of resin) The number average molecular weight (Mn) and mass average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8220GPC (manufactured by Tosoh Corporation) as the apparatus, two separation columns were connected in series, and for both packing materials, "TSK-GEL SUPER HZM-N" was connected in a pair and used. The measurement was carried out at an oven temperature of 40 °C, using a THF solution as the eluent, and at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent and 20 microliters were injected. All molecular weights are in terms of polystyrene conversion values.

[0186] (Acid value of the resin) To 0.5 - 1 g of the resin solution, 80 ml of acetone and 10 ml of water were added and stirred until uniformly dissolved. Using a 0.1 mol / L aqueous KOH solution as the titrant, titration was carried out using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mgKOH / g) of the resin solution. 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.

[0187] (Amine value (mgKOH / g) of the basic dispersion resin) The amine value of the basic dispersion resin is the value obtained by converting the measured total amine value (mgKOH / g) to non-volatile content in accordance with the method of ASTM D 2074.

[0188] (Ammonium salt value (mgKOH / g)) The ammonium salt value was determined by titrating with a 0.1 N aqueous silver nitrate solution using a 5% aqueous potassium chromate solution as the indicator, and then converting it to the equivalent of potassium hydroxide, indicating the ammonium salt value of the non-volatile content.

[0189] <Method for producing the micronized pigment> <Micronization of the colorant (A)> (Colorant (A-1)) 100 parts of C.I. Pigment Red 254 (Irgafure Red B-CF manufactured by BASF Japan), 10 parts of pigment derivative (b-1), 1000 parts of ground salt, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70 °C for 8 hours. This mixture was poured into 2000 parts of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80 °C to form a slurry. After repeating filtration and washing with water to remove salt and solvent, it was dried at 80 °C for 24 hours to obtain colorant (A-1).

[0190] (Colorant (A-2)) 500 parts of C.I. Pigment Red 177 (Chromophthal Red A2B manufactured by BASF Japan), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 120 °C for 8 hours. Next, this kneaded product was poured into 5 liters of warm water and stirred for 1 hour while heating to 70 °C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80 °C for a whole day and night to obtain colorant (A-2).

[0191] (Colorant (A-3)) 100 parts of C.I. Pigment Red 272 (Irgazin(r) Flame Red K 3800 manufactured by BASF Japan), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60 °C for 10 hours. Next, this mixture was poured into 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80 °C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and solvent, it was dried at 80 °C for a whole day and night to obtain colorant (A-3).

[0192] (Colorant (A-4)) 100 parts of C.I. Pigment Red 269 (Toner Magenta F8B manufactured by Clariant), 800 parts of sodium chloride, and 180 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 5 hours. This mixture was poured into 4000 parts of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80°C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and the solvent, it was dried at 80°C for 24 hours to obtain a colorant (A-4).

[0193] (Colorant (A-5)) 100 parts of C.I. Pigment Green 58 (FASTGEN GREEN A110 manufactured by DIC), 1200 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 6 hours. This kneaded product was poured into 3000 parts of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C for a whole day and night to obtain a colorant (A-5).

[0194] (Colorant (A-6)) 500 parts of C.I. Pigment Green 36 (Leonol Green 6YK manufactured by Toyo Color), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 120°C for 4 hours. Next, this kneaded product was poured into 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C for a whole day and night to obtain a colorant (A-6).

[0195] (Colorant (A-7)) 500 parts of C.I. Pigment Green 63 ("OPTLION GREEN 8885" manufactured by Toyo Color Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 120°C for 4 hours. Next, this kneaded material was put into 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C for a whole day and night to obtain a colorant (A-7).

[0196] (Colorant (A-8)) 100 parts of C.I. Pigment Blue 15:6 ("Leonol Blue ES" manufactured by Toyo Color Co., Ltd.), 1000 parts of crushed salt, and 100 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 50°C for 12 hours. This mixture was put into 3000 parts of warm water and stirred for about 1 hour with a high-speed mixer while heating to about 70°C to form a slurry. After repeating filtration and washing with water to remove salt and the solvent, it was dried at 80°C for 24 hours to obtain a colorant (A-8).

[0197] (Colorant (A-9)) 100 parts of C.I. Pigment Yellow 138 ("Parilotol Yellow K0961HD" manufactured by BASF Japan Ltd.), 800 parts of crushed salt, and 180 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 4 hours. This mixture was put into 3000 parts of warm water and stirred for about 1 hour with a high-speed mixer while heating to about 80°C to form a slurry. After repeating filtration and washing with water to remove salt and the solvent, it was dried at 80°C for 24 hours to obtain a colorant (A-9).

[0198] (Colorant (A-10)) 100 parts of C.I. Pigment Yellow 139 (Irgalite Yellow 2R-CF manufactured by BASF Japan), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60°C for 10 hours. Next, this mixture was poured into 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80°C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and the solvent, it was dried at 80°C for one day and night to obtain a colorant (A-10).

[0199] (Colorant (A-11)) 100 parts of C.I. Pigment Yellow 150 (Yellow Pigment E4GN manufactured by Lanxess), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 60°C for 10 hours. Next, this mixture was poured into 3 liters of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 80°C to form a slurry. After repeating filtration and washing with water to remove sodium chloride and the solvent, it was dried at 80°C for one day and night to obtain a colorant (A-11).

[0200] (Colorant (A-12)) 500 parts of C.I. Pigment Yellow 185 (Paliotol Yellow D1155 manufactured by BASF Japan), 500 parts of sodium chloride, and 250 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 120°C for 8 hours. Next, this kneaded product was poured into 5 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeating filtration and washing to remove sodium chloride and diethylene glycol, it was dried at 80°C for one day and night to obtain a colorant (A-12).

[0201] (Colorant (A-13)) 300 parts of dioxazine-based purple pigment Pigment Violet 23 (Leonogen Violet RL manufactured by Toyo Color Co., Ltd.) were added to 3000 parts of 96% sulfuric acid, stirred for 1 hour, and then poured into water at 5°C. After stirring for 1 hour, it was filtered, washed with warm water until the washing liquid became neutral, and dried at 70°C. 120 parts of the obtained acid pasting-treated pigment, 5 parts of pigment derivative (b-2), 1500 parts of ground salt, and 100 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 70°C for 20 hours. This mixture was added to 5000 parts of warm water, stirred with a high-speed mixer for about 1 hour while heating to about 70°C to form a slurry, filtered, and washed with water repeatedly to remove salt and solvent, and then dried at 80°C for 24 hours to obtain pigment (A-13).

[0202] (Dye solutions (a-1) to (a-3)) (Resin 1 having a cationic group in the side chain) 67.3 parts of methyl ethyl ketone was charged into a four-neck separable flask equipped with a thermometer, a stirrer, a distillation tube, and a cooler, and the temperature was raised to 75°C under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 6.5 parts of 2,2'-azobis(2,4-dimethylvaleronitrile), and 25.1 parts of methyl ethyl ketone were made uniform, then charged into a dropping funnel, attached to the four-neck separable flask, and dropped over 2 hours. Two hours after the dropping was completed, it was confirmed that the polymerization yield was 98% or more based on the non-volatile content and the weight average molecular weight (Mw) was 6830, and it was cooled to 50°C. 3.2 parts of methyl chloride and 22.0 parts of ethanol were added here, reacted at 50°C for 2 hours, then heated to 80°C over 1 hour, and further reacted for 2 hours. In this way, resin 1 having a cationic group in the side chain having an ammonium group of 47 mass% of the resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH / g.

[0203] (Dye 1) 30 parts by non-volatile content of a resin 1 having a cationic group in the side chain was added to 2000 parts of water, and after sufficient stirring and mixing, the mixture was heated to 60 °C. On the other hand, an aqueous solution was prepared by dissolving 10 parts of C.I. Acid Red 52 in 90 parts of water, and this was gradually added dropwise to the resin solution prepared above. After the addition, the mixture was stirred at 60 °C for 120 minutes to allow sufficient reaction. As a confirmation of the end point of the reaction, the reaction solution was dropped onto filter paper, and when the bleeding disappeared, it was judged that the end point was reached and a salt-forming compound was obtained. After allowing to cool to room temperature with stirring, suction filtration was carried out, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture with a dryer to obtain a colorant (Dye 1), which is a salt-forming compound of C.I. Acid Red 52 and resin 1 having a cationic group in the side chain. At this time, the content of the effective dye component derived from C.I. Acid Red 52 in the colorant (Dye 1) was 25% by mass.

[0204] (Dye 2) The colorant (Dye 2), which is a salt-forming compound of C.I. Acid Red 289 and resin 1 having a cationic group in the side chain, was obtained in the same manner as the production of the colorant (Dye 1) except that C.I. Acid Red 52 was changed to C.I. Acid Red 289. At this time, the content of the effective dye component derived from C.I. Acid Red 289 in the colorant (Dye 2) was 27% by mass.

[0205] (Dye 3) In a 1 L stainless steel reaction vessel equipped with a reflux tube, under a nitrogen atmosphere, 5.0 parts of C.I. Basic Violet 10 (BV10: manufactured by Tago Chemical Co., Ltd.: Rodamine B) and 1.6 parts of hydroxyethyl methacrylate (HEMA) were dissolved in 40 ml of dichloromethane, and 2.2 parts of 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide hydrochloride and 0.25 part of dimethylaminopyridine were added, followed by stirring at room temperature for 24 hours. The obtained dichloromethane solution was washed with water, dried under reduced pressure, and then purified by a silica gel column to obtain a colorant (Dye 3).

[0206] (Production of Dye Solution (a-1)) After stirring and mixing the following mixture to make it uniform, it was filtered through a filter with a pore size of 5.0 μm to prepare a dye solution (a-1). 12.5 parts of a colorant (Dye 1) 87.5 parts of PGMAc

[0207] (Production of Dye Solutions (a-2) and (a-3)) Dye solutions (a-2) and (a-3) were prepared in the same manner as the dye solution (a-1), except that the dye in the dye solution (a-1) was changed to Dye 2 and Dye 3.

[0208] <Basic Pigment Derivative> The following basic pigment derivatives were used. Basic Pigment Derivative (1)

Chemical Formula

Chemical Formula

Chemical Formula

[0209] (Production of Resin-Type Dispersant) (Production Example of Acidic Resin-Type Dispersant (B1-a-1)) 50.0 parts of tert-butyl acrylate, 45.0 parts of methyl methacrylate, and 5.0 parts of methacrylic acid were charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 °C, and a solution prepared by dissolving 0.1 part of 2,2'-azobisisobutyronitrile in 6.0 parts of 3-mercapto-1,2-propanediol in 70.7 parts of PGMAc was added, and the reaction was carried out for 10 hours. It was confirmed by non-volatile content measurement that 95% or more had reacted. Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 38.0 parts of PGMAc, and 0.2 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120°C for 5 hours. Then, 12.1 g of 3-methoxybutanol was added, and the mixture was reacted at 120°C for 3 hours. The reaction was terminated after confirming by acid value measurement that 98% or more of the acid anhydride was half-esterified. After the reaction was completed, PGMAc was added to adjust the nonvolatile content to 40% by mass, and a solution of a dispersant (B1-a-1) with an acid value of 110 mg KOH / g and a weight-average molecular weight of 9000 was obtained.

[0210] (Production Example of Acidic Resin-Type Dispersant (B1-a-2)) Into a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 20.0 parts of t-butyl acrylate, 45.0 parts of methyl methacrylate, 30.0 parts of ethyl acrylate, and 5.0 parts of methacrylic acid were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80°C, and a solution prepared by dissolving 0.1 part of 2,2'-azobisisobutyronitrile in 6.0 parts of 3-mercapto-1,2-propanediol and 70.7 parts of PGMAc was added, and the mixture was reacted for 10 hours. It was confirmed by nonvolatile content measurement that 95% of the reaction had occurred. Next, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), 38.0 parts of PGMAc, and 0.2 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the mixture was reacted at 120°C for 5 hours. Then, 12.1 g of 3-methoxybutanol was added, and the mixture was reacted at 120°C for 3 hours. The reaction was terminated after confirming by acid value measurement that 98% or more of the acid anhydride was half-esterified. After the reaction was completed, PGMAc was added to adjust the nonvolatile content to 40% by mass, and a solution of an acidic resin-type dispersant (B1-a-2) with an acid value of 105 mg KOH / g and a weight-average molecular weight of 9400 was obtained.

[0211] (Production Example of Acidic Resin-Type Dispersant (B1-a-3)) Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 6 parts of 3-mercapto-1,2-propanediol, 14.5 parts of pyromellitic dianhydride (manufactured by Daicel Chemical Industries, Ltd.), and 70.8 parts of PGMAc were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 100 °C and reacted for 5 hours. Then, 12.1 g of 3-methoxybutanol was added and reacted at 120 °C for 3 hours. After confirming by acid value measurement that 98% or more of the acid anhydride was half-esterified, the temperature inside the system was cooled to 70 °C, 50.0 parts of t-butyl acrylate and 50.0 parts of methyl methacrylate were charged, and 38.0 parts of PGMAc in which 0.1 part of 2,2'-azobisisobutyronitrile was dissolved was added and reacted for 10 hours. After confirming by non-volatile content measurement that the polymerization had proceeded 95%, the reaction was terminated. After the reaction was completed, PGMAc was added to adjust the non-volatile content to 40% by mass, and a solution of a dispersant (B1-a-3) with an acid value of 93 mgKOH / g and a weight average molecular weight of 10,800 was obtained.

[0212] (Production of acidic resin type dispersant (B1-a-4: comb type)) Into a reaction vessel equipped with a gas inlet tube, a temperature sensor, a condenser, and a stirrer, 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of iso-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc (PGMAc) were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 °C, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 °C and reacted for 7 hours while adding a solution prepared by adding 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of PGMAc. After confirming by non-volatile content measurement that 95% had reacted, 19 parts of pyromellitic dianhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 100 °C for 7 hours. After confirming by acid value measurement that 98% or more of the acid anhydride groups were half-esterified, the reaction was terminated, and PGMAc was added for dilution to a non-volatile content of 40% by non-volatile content measurement, and a resin type dispersant (B1-a-4) solution with an acid value of 70 mgKOH / g and a weight average molecular weight of 8,500 was obtained.

[0213] (Production of Acidic Resin Dispersant (B1-a-5: Comb-shaped, Thermally Crosslinked)) Into a reaction vessel equipped with a gas introduction tube, thermometer, condenser, and stirrer, 160 parts of n-butyl acrylate, 40 parts of Karenz MOI-BM (manufactured by Showa Denko KK: containing a blocked isocyanate group which is a thermally crosslinkable group), 50 parts of PGMAc, and 50 parts of cyclohexanone were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated to 80 °C, 12 parts of 3-mercapto-1,2-propanediol was added, and the reaction was carried out for 12 hours. It was confirmed by non-volatile content measurement that 95% of the reaction had occurred. Next, 19 parts of pyromellitic dianhydride, 231 parts of cyclohexanone, and 0.40 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 100 °C for 7 hours. It was confirmed by acid value measurement that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. The non-volatile content was adjusted to 40% with PGMAc to obtain a resin-type dispersant (B1-a-5) containing a blocked isocyanate group which is a thermally crosslinkable group with an acid value of 42 mgKOH / g and a weight average molecular weight of 9000.

[0214] (Production of Acidic Resin Dispersant (B1-a-6: Comb-shaped, (Meth)acryloyl Group-Containing)) Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic dianhydride, 650 parts of PGMAc, and 0.2 part of monobutyltin oxide as a catalyst were charged. After purging with nitrogen gas, the mixture was reacted at 120 °C for 5 hours (first step). It was confirmed by measuring the acid value that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of non-volatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, 200 parts of methyl acrylate, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged. The inside of the reaction vessel was heated to 80 °C, 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours (second step). It was confirmed by measuring the non-volatile content that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were charged, and the reaction was carried out until the disappearance of the peak at 2270 cm-1 based on the isocyanate group was confirmed by IR (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and the non-volatile content was adjusted with PGMAc to obtain a resin-type dispersant (B1-a-6) solution containing 40% non-volatile content of (meth)acryloyl groups. The acid value of the obtained dispersant was 68, the unsaturated double bond equivalent was 1593, and the weight average molecular weight was 13000.

[0215] (Production of acidic resin-type dispersant (B1-a-7: linear)) An 80 parts of methyl methacrylate, 120 parts of ethyl acrylate, and 40 parts of methoxypropyl acetate were charged into a reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, and the vessel was purged with nitrogen gas. The inside of the reaction vessel was heated to 80 °C, 4.4 parts of 3-mercapto-1,2-propanediol was added, and then 0.2 part of 2,2'-azobisisobutyronitrile was added in 20 portions at 30-minute intervals. The reaction was carried out at 80 °C for 12 hours, and it was confirmed by non-volatile content measurement that 95% of the reaction had occurred. Next, 12 parts of trimellitic anhydride, 190 parts of methoxypropyl acetate, and 0.40 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was carried out at 120 °C for 2 hours and at 80 °C for 5 hours. It was confirmed by titration that more than 90% of the acid anhydride was half-esterified, and a resin-type dispersant (B1-a-7) with an acid value of 44 mgKOH / g per non-volatile content was obtained. Furthermore, a dispersant (B1-a-7) solution with a non-volatile content of 40% was obtained by adjusting the non-volatile content with PGMAc.

[0216] (Production of acidic resin-type dispersant (B1-a-8: linear, containing tertiary butyl group and oxetane group, which is thermally crosslinked)) Into a reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 3 parts of trimellitic anhydride, 1 part of 3-mercapto-1,2-propanediol, 50 parts of PGMAc, and 0.1 part of dimethylbenzylamine were charged. After purging with nitrogen gas, the inside of the reaction vessel was heated to 120 °C and reacted for 4 hours, and then reacted at 80 °C for 2 hours. Further, 30 parts of tertiary butyl acrylate, 20 parts of ETERNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate, manufactured by Ube Industries, Ltd.), 5 parts of methacrylic acid, 40 parts of ethyl acrylate, and 10 parts of PGMAc were charged, and 0.2 part of 2,2'-azobisisobutyronitrile was added in 15 portions at 30-minute intervals while maintaining the inside of the reaction vessel at 80 °C. One hour after the final addition, nonvolatile content measurement was performed, and it was confirmed that 95% of the monomer had reacted. PGMAc was added for dilution so that the nonvolatile content became 40% by nonvolatile content measurement, and a resin-type dispersant (B1-a-8) solution having a tertiary-butyl group and an oxetane group, which is a thermally crosslinked product with an acid value of 51 mgKOH / g per nonvolatile content and a weight average molecular weight (Mw) of 24,000, was obtained.

[0217] (Production of acidic resin-type dispersant (B1-a-9)) Into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, 62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin(IV) oxide as a catalyst were charged. After purging with nitrogen gas, it was heated and stirred at 120 °C for 4 hours. After confirming by nonvolatile content measurement that 98% had reacted, 73.3 parts of pyromellitic anhydride was added and reacted at 120 °C for 2 hours. By measuring the acid value, it was confirmed that 98% or more of the acid anhydride was half-esterified, and the reaction was terminated. A dispersant (B1-a-9) solution with a nonvolatile content of 40% was obtained by adjusting the nonvolatile content with PGMAc. The obtained dispersant was a white solid at room temperature, and the acid value was 49 mgKOH / g.

[0218] (Production of other acidic resin-type dispersant (B1-a-10)) A separable four-necked flask was equipped with a thermometer, a condenser, a nitrogen gas inlet tube, and a stirring device, and 1500 parts of cyclohexanone was charged. After heating to 80 °C and purging the inside of the reaction vessel with nitrogen, 120 parts of methyl methacrylate, 210 parts of n-butyl methacrylate, 90 parts of 2-hydroxyethyl methacrylate, 60 parts of methacrylic acid, 120 parts of para-cumylphenol ethylene oxide-modified acrylate (“Aronix M-110” manufactured by Toagosei Co., Ltd.), 6 parts of acid phosphoxyethyl methacrylate, and 30 parts of 2,2'-azobisisobutyronitrile were mixed and the resulting solution was added dropwise over 2 hours through a dropping tube. After completion of the dropwise addition, the reaction was continued for an additional 3 hours to obtain an acidic resin type dispersant (B1-a-10) solution having a nonvolatile content of 40% and a weight average molecular weight of 24,000.

[0219] (Production of basic resin type dispersant (B1-b-1)) Into a reactor equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged. While flowing nitrogen, the mixture was stirred at 50 °C for 1 hour, and the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 133 parts of PGMAc were charged. Under a nitrogen stream, the temperature was raised to 110 °C to initiate the polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate was 98% or more in terms of non-volatile content. Next, 61 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as the second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were added to this reactor, and the mixture was stirred while maintaining the temperature at 110 °C in a nitrogen atmosphere to continue the reaction. Two hours after the addition, the polymerization solution was sampled for non-volatile content measurement, and it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or more in terms of non-volatile content, and the reaction solution was cooled to room temperature to stop the polymerization. As a result of GPC measurement, the polymer had a mass average molecular weight of 20,000 and a molecular weight distribution Mw / Mn of 1.4, and the reaction conversion rate was 98.5%. In this way, a basic resin-type dispersant (B1-b-1) with an amine value of 169.8 mgKOH / g per non-volatile content was obtained. After cooling to room temperature, about 2 g of the resin-type dispersant solution was sampled and heated and dried at 180 °C for 20 minutes to measure the non-volatile content. PGMAc was added to the previously synthesized basic resin-type dispersant (B1-b-1) so that the non-volatile content became 40% by mass to prepare a solution of the basic resin-type dispersant (B1-b-1) of the A-B-A block polymer.

[0220] (Production of basic resin-type dispersant (B1-b-2)) Into a reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer, 133 parts of PGMAc were charged, and the temperature was raised to 110 °C while purging with nitrogen. Into a dropping funnel, 177 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate, 3 parts of methyl acrylate, 20 parts of 2-hydroxyethyl methacrylate, 61 parts of PGMAc, and 6 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) were charged, stirred until homogeneous, then added dropwise to the reaction vessel over 2 hours, and the reaction was continued at the same temperature for 3 hours. In this way, a basic resin type dispersant (B1-b-2) with an amine value of 201 mgKOH / g per non-volatile content and a number average molecular weight of 3,800 (Mn) was obtained. The basic resin type dispersant (B1-b-2) solution was diluted in the same manner so that the non-volatile content became 40% by mass to prepare a basic resin type dispersant (B1-b-2) solution of a random polymer.

[0221] <Production Example of Binder Resin (B2)> (Preparation of Binder Resin (B2-1) Solution) 196 parts of cyclohexanone were charged into a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirring device, the temperature was raised to 80 °C, and after purging the inside of the reaction vessel with nitrogen, a mixture of 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of para-cumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise from the dropping tube over 2 hours. After completion of the dropwise addition, the reaction was continued for another 3 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 parts of the resin solution were sampled, heated and dried at 180 °C for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content became 20% to prepare a binder resin (B2-1) solution. The weight average molecular weight (Mw) was 26,000.

[0222] (Preparation of Binder Resin (B2-2) Solution) 370 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirring device, heated to 80 °C, and after replacing the air in the flask with nitrogen, from the dropping tube, 18 parts of para-cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile were added dropwise over 2 hours. After the addition, the reaction was further carried out at 100 °C for 3 hours, then a solution prepared by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was continued at 100 °C for 1 hour. Next, the air in the container was replaced with air, 0.5 part of tris(dimethylamino)phenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (equivalent to 100 mol% of glycidyl groups) in the above container, and the reaction was continued at 120 °C for 6 hours until the non-volatile acid value reached 0.5, and the reaction was terminated to obtain a solution of an acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (equivalent to 100 mol% of the generated hydroxyl groups) and 0.5 part of triethylamine were added and reacted at 120 °C for 3.5 hours to obtain a solution of an acrylic resin. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 °C for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content became 20% by mass to prepare a binder resin (B2-2) solution. The weight average molecular weight (Mw) was 19,000.

[0223] (Preparation of Binder Resin (B2-3) Solution) 207 parts of cyclohexanone was charged into a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping funnel, and a stirrer, and the temperature was raised to 80 °C. After replacing the air in the reaction vessel with nitrogen, a mixture of 20 parts of methacrylic acid, 20 parts of p-cumylphenol ethylene oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise from the dropping funnel over 2 hours. After completion of the addition, the reaction was continued for an additional 3 hours to obtain a copolymer resin solution. Next, while stopping the nitrogen gas and injecting dry air for 1 hour with stirring, the total amount of the obtained copolymer solution was cooled to room temperature, and then a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko K.K.), 0.08 part of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70 °C over 3 hours. After completion of the addition, the reaction was continued for an additional 1 hour to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180 °C for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content became 20% to prepare a binder resin (B2-2). The weight average molecular weight (Mw) was 18,000.

[0224] (Preparation of binder resin (B2-4) solution) A separable flask equipped with a cooling pipe was prepared as a reaction vessel. On the other hand, as a monomer dropping tank, 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, 120 parts of methyl methacrylate, 4 parts of t-butylperoxy-2-ethylhexanoate (Perbutyl O manufactured by NOF Corporation), and 40 parts of PGMAc were thoroughly stirred and mixed to prepare a mixture. As a chain transfer agent dropping tank, 8 parts of n-dodecanethiol and 32 parts of PGMAc were thoroughly stirred and mixed to prepare a mixture. 395 parts of PGMAc was charged into the reaction vessel, and after nitrogen substitution, it was heated in an oil bath with stirring to raise the temperature of the reaction vessel to 90°C. After the temperature of the reaction vessel stabilized at 90°C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was carried out over 135 minutes while maintaining the temperature at 90°C. Sixty minutes after the completion of dropping, heating was started to raise the temperature of the reaction vessel to 110°C. After maintaining at 110°C for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of an oxygen / nitrogen = 5 / 95 (volume ratio) mixed gas was started. Next, 70 parts of glycidyl methacrylate, 0.4 part of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 part of triethylamine were charged into the reaction vessel, and the reaction was carried out at 110°C for 12 hours as it was. Thereafter, 150 parts of PGMAc was added and cooled to room temperature. Approximately 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized resin solution so that the non-volatile content became 20% by mass to obtain a binder resin (B2-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per non-volatile content was 2 mg KOH / g.

[0225] <Method for producing a colored composition> [Production Example 1] (Preparation of colored composition (X-1)) The following mixture was stirred and mixed uniformly, and then dispersed with an Eiger mill (Mini Model M-250 MKII manufactured by Eiger Japan Co., Ltd.) using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a filter with a pore size of 5.0 μm to prepare a colored composition (X-1) with a non-volatile component of 20.0% by mass. Pigment (A-1): 15.0 parts Pigment Derivative (b-1): 1.0 part Acidic Dispersion Resin ((B1-a-1): 40% Non-volatile Liquid): 10.0 parts Solvent (E2-1): 74.0 parts

[0226] [Production Examples 2 to 30] (Preparation of Coloring Compositions (X-2 to X-30)) Coloring compositions (X-2 to X-30) with a non-volatile content of 20% were prepared in the same manner as in Formulation Example 1, except that the types and masses of the materials were changed as described in Table 1.

[0227]

Table 1

[0228] [Example 1] (Preparation of Photosensitive Coloring Composition (Y-1)) The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition (X-1) with a non-volatile content of 16.7%. Coloring Composition (X-1: Non-volatile Content 20.0%): 45.0 parts Coloring Composition (X-25: Non-volatile Content 20.0%): 15.0 parts Binder Resin (B2-1: Non-volatile Content 20.0%): 3.0 parts Polymerizable Compound (C-1): 1.2 parts Photoinitiator (D1-1-1): 0.3 part Leveling Agent (F: Non-volatile Content 3%): 0.5 part Thermosetting Compound (Ex-1): 0.1 part Thermosetting Compound (Ex-2): 0.1 part Sensitizer (F): 0.1 part Thiol-based Chain Transfer Agent (G): 0.1 part Polymerization Inhibitor (H): 0.01 part Ultraviolet Absorber (I): 0.04 part Storage Stabilizer (L): 0.05 part Adhesion Improver (M): 0.1 part Solvent (E1-1): 3.5 parts Solvent (E2-1): 28.9 parts

[0229] [Examples 2 to 64, Comparative Examples 1 to 4] (Photosensitive coloring composition (Y-2 to Y-68)) Except for changing the types and masses of the materials as described in Tables 2-1 and 2-2, the photosensitive coloring compositions (Y-2 to Y-68) were prepared in the same manner as in Example 1.

[0230]

Table 2-1

[0231]

Table 2-2

[0232] Each raw material in the table is as follows. (Polymerizable compound (C)) (C1-a) EO-modified (12) dipentaerythritol hexaacrylate [KAYARAD DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.)]

Chemical formula

[0233] (C1-b) Acrylic acid ester of EO-modified trimethylolpropane [Aronix M-350 (manufactured by Toagosei Co., Ltd.)]

Chemical formula

[0234] (C1-c) Polypropylene glycol diglycidyl ether-acrylic acid adduct [Epoxy ester 200PA(N) (manufactured by Kyoeisha Chemical Co., Ltd.)]

Chemical formula

[0235] <Photoinitiator (D)> (D-1) 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Omnirad 907 (manufactured by IGM Resins)] (D-2) 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Omnirad 379EG (manufactured by IGM Resins)] (D-3) 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide [Omnirad TPO (manufactured by IGM Resins)] (D-4) 2,2'-Bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole [Biimidazole (manufactured by Koganei Chemical Co., Ltd.)] (D-5) p-Dimethylaminoacetophenone [DMA (manufactured by Daiki Fine Co., Ltd.)] [Omnirad 2959 (manufactured by IGM Resins)] (D-6) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Omnirad 819 (manufactured by IGM Resins)] The above (D-1) to (D-6) were each mixed in the same amount to obtain a photoinitiator (D-M). (D1-2-1) Mixture of oxime ester-based photoinitiators having a carbazole skeleton, which is a mixture of four photoinitiators shown in the following formula (2) in equal amounts. Formula (2) [Chemical formula]

[0236] (D1-2-2) An oxime ester-based photoinitiator having a carbazole skeleton represented by the following formula (3) [Chemical formula]

[0237] (D1-2-3) A mixture obtained by mixing in equal amounts an oxime ester-based photoinitiator having three carbazole skeletons represented by the following formula (4) Formula (4) [Chemical formula]

[0238] (D1-1―1) An oxime ester-based photoinitiator having a diphenyl skeleton represented by the following formula (5) Formula (5) [Chemical formula]

[0239] (D1-1―2) An oxime ester-based photoinitiator having a diphenyl skeleton represented by the following formula (6) Formula (6) [Chemical formula]

[0240] (D1-3) An oxime ester-based photoinitiator having a fluorene skeleton represented by the following formula (7) Formula (7) [Chemical formula]

[0241] (D1-4) A photoinitiator having two oxime ester groups represented by the following formula (8) Formula (8) [Chemical formula]

[0242] <Solvent (E)> (E1-1) Diethylene glycol monoethyl ether (boiling point 202 °C / vapor pressure 13 Pa) (E1-2) Dipropylene glycol monobutyl ether (boiling point 229 °C / vapor pressure 8 Pa) (E1-3) Tripropylene glycol methyl ether (boiling point 243 °C / vapor pressure 3 Pa) (E1-4) 1,2-Butanediol (boiling point 193 °C / vapor pressure 2.7 Pa) (E1-5) 1,3-Butanediol (boiling point 207 °C / vapor pressure 8 Pa) (E2-1) PGMAc (boiling point 146 °C / vapor pressure 490 Pa) (E2-2) Cyclopentanone (boiling point 131 °C / vapor pressure 1150 Pa) (E3-1) 3-Methoxybutanol (boiling point 161 °C / vapor pressure 17 Pa) (E3-2) 1-Butoxy-2-propanol (boiling point 170 °C / vapor pressure 139 Pa) (E4-1) Dipropylene glycol methyl normal propyl ether (boiling point 203 °C / vapor pressure 80 Pa)

[0243] <Thermosetting compound (Ex)> · Thermosetting compound (Ex-1) (Ex-1-1) 1,2-Epoxy-4-(2-oxiranyl) cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol [EHPE-3150 (manufactured by Daicel Corporation)] (Ex-1-2) Glycidyl etherified epoxy compound of sorbitol [Denacol EX611 (manufactured by Nagase ChemteX Corporation)] (Ex-1-3) Triglycidyl isocyanurate (Ex-1-1) to (Ex-1-3) were each mixed in the same amount to obtain a thermosetting compound (Ex-1). · Thermosetting compound (Ex-2): 3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane [Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

[0244] <Sensitizer (F)> (F-1) 2,4-Diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)] (F-2) 4,4'-Bis(diethylamino)benzophenone [Chemark DEABP (manufactured by Chemark Chemical)] As described above, (F-1) and (F-2) were each mixed in the same amount to obtain the sensitizer (F).

[0245] <Thiol-based chain transfer agent (G)> (G-1) Trimethylolethane tris(3-mercaptobutyrate) [TEMB (manufactured by Showa Denko KK)] (G-2) Trimethylolpropane tris(3-mercaptobutyrate) [TPMB (manufactured by Showa Denko KK)] (G-3) Pentaerythritol tetrakis(3-mercaptopropionate) [PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (G-4) Trimethylolpropane tris(3-mercaptopropionate) [TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (G-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)] As described above, (G-1) to (G-5) were each mixed in the same amount to obtain the thiol-based chain transfer agent (G).

[0246] <Polymerization inhibitor (H)> (H-1) 3-Methylcatechol (H-2) Methylhydroquinone (H-3) tert-Butylhydroquinone As described above, (H-1) to (H-3) were each mixed in the same amount to obtain the polymerization inhibitor (H).

[0247] <Ultraviolet absorber (I)> (I-1) 2-[4-[(2-Hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine [TINUVIN 400 (manufactured by BASF Japan Ltd.)] (I-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN 900 (manufactured by BASF Japan Ltd.)] The above (I-1) and (I-2) were each mixed in the same amount to obtain an ultraviolet absorber (I).

[0248] <Antioxidant (J)> (J-1) Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (J-2) Dioctadecyl 3,3'-thiodipropionate (J-3) Tris[2,4-di-(t)-butylphenyl]phosphine (J-4) Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (J-5) p-Octylphenyl salicylate The above (J-1) to (J-5) were each mixed in the same amount to obtain an antioxidant (J).

[0249] <Leveling agent (K)> 1 part of "BYK-330" manufactured by BYK-Chemie GmbH, 1 part of "FZ-2122" manufactured by DOW Chemical Company, and A mixed solution obtained by dissolving 1 part of "Emulgen 103" manufactured by Kao Corporation in 97 parts of PGMAc.

[0250] <Storage stabilizer (L)> (L-1) 2,6-Bis(1,1-dimethylethyl)-4-methylphenol ["BHT" manufactured by Honshu Chemical Industry Co., Ltd.] (L-2) Triphenylphosphine ["TPP" manufactured by Kitakyo Chemical Industry Co., Ltd.] The above (L-1) and (L-2) were each mixed in the same amount to obtain a storage stabilizer (L).

[0251] <Adhesion improver (M)> (M-1) "KBM-5103 (manufactured by Shin-Etsu Chemical Co., Ltd.)" (M-2) 3-Glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (M-3) 3-Methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (M-4) N-2-(Aminoethyl)-3-aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (M-5) 3-Mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)] The above (M-1) to (M-5) were each mixed in the same amount to obtain the adhesion improver (M).

[0252] <Evaluation of the photosensitive coloring composition> The obtained photosensitive coloring compositions (Y-1 to Y-68) were evaluated by the following method. The results are shown in Table 4. Each test was conducted by the following method. The test results are shown in Table 4. The meaning of the evaluation ranks is as follows. 〇: Good △: Practicable ×: Not suitable for practical use

[0253] <Formation of the filter segment> A black matrix was pattern-processed on a 100 mm × 100 mm, 0.7 mm thick glass substrate. The obtained photosensitive coloring composition was applied onto the substrate using a spin coater and dried at 90 °C for 90 seconds to remove the solvent, obtaining a film with a film thickness of 2.4 μm. Next, through a photomask having a predetermined pattern on the film, an ultra-high pressure mercury lamp was used at 100 mJ / cm 2It was irradiated with ultraviolet rays and spray-developed with an alkaline developer composed of a 0.2 mass% aqueous sodium carbonate solution to remove the uncured portion and form a desired pattern. Subsequently, heat treatment was performed in an oven at 230 °C for 20 minutes to form a filter segment. The film thickness of the coating film was measured using a Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

[0254] <Evaluation of development residue> The obtained filter segment was observed with a microscope (Olympus Optical Co., Ltd. "BX-51") to confirm the presence or absence of development residue. The evaluation was performed by calculating the remaining area of the residue in a 50 μm × 50 μm area after removing the uncured portion in the coating film with an alkaline developer, and the evaluation was as follows. ○: Less than 100 μm 2 Less than △: 100 μm or more and less than 500 μm 2 500 μm or more 2 Less than ×: 500 μm or more 2 or more

[0255] <Evaluation of striation and surface smoothness> Using an etching method on the entire surface of an 8-inch (1 inch = 2.54 cm) diameter silicon wafer, a square pattern with a vertical and horizontal dimension of 50 μm and a height of 0.8 μm was formed over the entire surface in the range of 2000 μm in length and 3000 μm in width. The space between each pattern was separated by a groove with a width of 2.5 μm. Subsequently, the obtained photosensitive coloring composition was applied by spin coating to form a film, and then heated on a hot plate at 100 °C for 120 seconds for drying. Thereafter, it was further heated on a hot plate at 200 °C for 300 seconds for post-baking. After cooling to room temperature, a test substrate with a film thickness of 1.0 μm was produced. The steps located at positions 1 to 28 on the silicon wafer shown in Figure 3 were selected, and the corners of these steps were observed with an optical microscope (50 times magnification). Among the four corners of the step, the corner of the portion farthest from the center of the silicon wafer was visually observed, and striation (the presence or absence of radial streak unevenness) and coating unevenness were evaluated according to the following criteria. (Evaluation of striation) 〇: Striation was not observed at any of the positions 1 to 28 in Figure 3. △: In the regions 1 to 28 in FIG. 3, the number of regions where striations were observed was less than 10. ×: In the regions 1 to 28 in FIG. 3, the number of regions where striations were observed was 10 or more.

[0256] (Evaluation of surface smoothness) The smoothness of the patterned surface of the test substrate was evaluated based on the presence or absence of coating unevenness. 〇: No coating unevenness was observed in any of the regions 1 to 28 in FIG. 3. △: In the regions 1 to 28 in FIG. 3, the number of regions where coating unevenness was observed was less than 10. ×: In the regions 1 to 28 in FIG. 3, the number of regions where coating unevenness was observed was 10 or more.

[0257]

Table 3-1

[0258]

Table 3-2

[0259] In the table, the solvent content indicates the content in the photosensitive composition.

Explanation of symbols

[0260] 10 Liquid crystal display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing plate 30 Backlight unit 31 White LED light source LC Liquid crystal 100 Infrared sensor 110 Light-receiving element 111 Infrared absorption filter 112 Color filter 113 Infrared absorption and transmission filter 114 Resin film 115 Microlens 116 Flat film

Claims

1. A photosensitive coloring composition for color filters, comprising a colorant (A), a resin (B), a polymerizable monomer (C), a photopolymerization initiator (D), and a solvent (E), The solvent (E) contains 0.5 to 15% by mass of a solvent (E1) satisfying the following (1) and (2) in 100% by mass of the photosensitive coloring composition: A photosensitive coloring composition for color filters, comprising 15 to 80 mass % of a solvent (E2) satisfying the following (3) and (4) based on 100 mass % of the photosensitive coloring composition: (1) A boiling point at atmospheric pressure (1013.25 hPa) of 180°C or higher and lower than 250°C (2) A vapor pressure at 20°C of 1 to less than 15 Pa (3) A boiling point at atmospheric pressure (1013.25 hPa) of 120°C or higher and lower than 150°C (4) A vapor pressure at 20°C of 400 or more and less than 1,200 Pa.

2. The photosensitive coloring composition for color filters according to claim 1, further comprising 0.5 to 15 mass% of a solvent (E3) that satisfies the following (5) and (6) in 100 mass% of the photosensitive coloring composition. (5) A boiling point at atmospheric pressure (1013.25 hPa) of 150°C or higher but lower than 180°C (6) A vapor pressure at 20°C of 15 to less than 400 Pa

3. The photosensitive coloring composition for color filters according to claim 1, wherein the solvent (E1) is selected from the group consisting of diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monobutyl ether, tripropylene glycol methyl ether, 1,2-butanediol, 1,3-butanediol, and 1,4-butanediol.

4. A color filter having filter segments formed from the photosensitive coloring composition for color filters according to any one of claims 1 to 4.

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

6. A liquid crystal display device comprising the color filter according to claim 4.

7. An infrared sensor comprising the color filter according to claim 4.

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