Photosensitive coloring composition, cured film using the same, color filter, image display device, and solid-state imaging device

Abstract

To provide a photosensitive coloring composition which is excellent in chemical resistance even in low-temperature heating treatment of 150°C or lower, and enables formation of a fine pattern.SOLUTION: A photosensitive coloring composition that is used in pattern formation of a color filter by a photolithography method of curing a pattern in a heating step of 150°C or lower after development contains a pigment (A), a resin (B), a photopolymerization initiator (C), and a polymerizable compound (D), wherein the resin (B) contains a resin (B1) containing a block isocyanate group-containing constitutional unit, and a resin (B2) containing a (meth)acryloyl group-containing vinyl polymer moiety.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a photosensitive coloring composition corresponding to a low-temperature heating process of 150°C or lower.

Background Art

[0002] The film or fine pattern of a color filter used in an image display device such as a liquid crystal display device or an organic EL display device and a solid-state imaging device requires optical properties such as transparency, while chemical resistance and the like are required when performing post-processes such as the formation and assembly of other members. Therefore, it is known to add a thermosetting agent to the photosensitive coloring composition in advance and perform photocuring and thermosetting to form a film or fine pattern excellent in chemical resistance. (For example, Patent Documents 1 and 2)

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, with the advancement of the flexibility and wearability of image display devices, there is an increasing need to fabricate elements using flexible substrates instead of the rigid glass substrates that have been conventionally used. Since many flexible substrates are made of organic materials and have lower heat resistance than glass substrates, it is necessary to lower the thermosetting temperature. For example, in the production of color filters, thermosetting has been carried out at about 200 to 230 °C, but when using a plastic flexible substrate, it is necessary to lower the thermosetting temperature to 150 °C or lower due to the heat resistance problem. However, in conventional compositions, since thermosetting does not proceed sufficiently, by using a large amount of a highly sensitive photocurable material, the film crosslinking degree can be increased to obtain the desired heat resistance, but on the other hand, there has been a problem that it becomes difficult to form fine patterns.

[0005] An object of the present invention is to provide a photosensitive coloring composition that has excellent chemical resistance and can form fine patterns even with a low-temperature heat treatment of 150 °C or lower.

Means for Solving the Problems

[0006] The photosensitive coloring composition of the present invention is a photosensitive coloring composition used for forming a pattern of a color filter by a photolithography method that cures the pattern in a heating step of 150 °C or lower after development, containing a pigment (A), a resin (B), a photopolymerization initiator (C), and a polymerizable compound (D), wherein the resin (B) contains a resin (B1) containing a blocked isocyanate group-containing structural unit and a resin (B2) containing a (meth)acryloyl group-containing vinyl polymer moiety.

Effects of the Invention

[0007] According to the present invention described above, a photosensitive coloring composition that has excellent chemical resistance and can form fine patterns even with a low-temperature heat treatment of 150 °C or lower can be provided. Further, the present invention can provide a color filter, an image display device such as a liquid crystal display device and an organic EL display device, and a solid-state imaging device based on the photosensitive coloring composition.

Modes for Carrying Out the Invention

[0008] 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." listed in this specification means Color Index (C.I.). The photolithography method is a manufacturing method in which ultraviolet exposure is performed on a film through a photomask, and then the unexposed portion of ultraviolet rays is removed by development to form a pattern. In the manufacture of a color filter, generally, a heating step (also referred to as post-bake) is performed after the pattern formation.

[0009] The photosensitive coloring composition of the present invention is a photosensitive coloring composition used for forming a pattern of a color filter by a photolithography method in which the pattern is cured in a heating step at 150 °C or lower after development, containing a pigment (A), a resin (B), a photopolymerization initiator (C), and a polymerizable compound (D), wherein the resin (B) contains a resin (B1) containing a blocked isocyanate group-containing structural unit and a resin (B2) containing a (meth)acryloyl group-containing vinyl polymer moiety. The photosensitive coloring composition of the present invention is preferably used for forming a cured film, a color filter, etc. Further, the cured film and the color filter are preferably used in applications such as an image display device such as a liquid crystal display device and an organic EL display device, and a solid-state imaging device.

[0010] The photosensitive coloring composition of the present invention contains a resin (B1) containing a blocked isocyanate group-containing structural unit and a resin (B2) containing a (meth)acryloyl group-containing vinyl polymer moiety as the resin (B). The reason for this is that if excessive photocuring is carried out in an attempt to obtain sufficient chemical resistance with the resin (B2) containing a vinyl polymer moiety having a (meth)acryloyl group, the line width of the pattern after development becomes thick and the resolution decreases, making it difficult to form a fine pattern. However, by combining with the resin (B1) containing a blocked isocyanate group-containing structural unit, while maintaining appropriate photocurability, the desired curability can be obtained even in a low-temperature heating step of 150°C or lower, thus improving chemical resistance. Therefore, the photosensitive coloring composition has improved chemical resistance, low-temperature curability, and fine pattern formation.

[0011] <Pigment (A)> The photosensitive coloring composition of the present invention contains a pigment (A) as a colorant. Examples of the pigment (A) include organic pigments and inorganic pigments. The pigment is preferably a pigment having high color development and high heat resistance, particularly a pigment having high thermal decomposition resistance, and usually an organic pigment is used. Specific examples of the organic pigment are shown by the Color Index number below.

[0012] 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, pigments described in JP-A No. 2014-134712, pigments described in Patent No. 6368844, and the like. Among these, from the viewpoints of heat resistance, light resistance, and transmittance, C.I. Pigment Red 48:1, 122, 177, 224, 242, 269, 254, 291, 295, 296, pigments described in JP-A No. 2014-134712, and pigments described in Patent No. 6368844 are preferable, and C.I. Pigment Red 177, 254, 269, 291, 295, 296, pigments described in JP-A No. 2014-134712, and pigments described in Patent No. 6368844 are more preferable.

[0013] Examples of orange pigments include C.I. Pigment Orange 36, 38, 43, 64, 71, 73, etc.

[0014] Examples of yellow pigments include 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, pigments described in JP-A Nos. 2012-226110, 2017-171912, 2017-171913, 2017-171914, 2017-171915, etc. Among these, C.I. Pigment Yellow 138, 139, 150, 185, 231, 233, and the pigments described in JP-A No. 2012-226110 are preferred.

[0015] Examples of green pigments include 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. Among these, C.I. Pigment Green 36, 58, 59, 62, 63 are preferred.

[0016] The cyan 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. Among these, C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 are preferred.

[0017] The purple 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. Among these, C.I. Pigment Violet 19, 23 are preferred.

[0018] The black pigments include, for example, C.I. Pigment Black 1, 6, 7, 12, 20, 31, 32, etc. Also, the compounds described in JP-T-2010-534726, JP-T-2012-515233, JP-T-2012-515234, JP-A-1-170601, JP-A-2-34664, etc. are also included. Note that the black pigments include inorganic pigments.

[0019] The inorganic pigments include, for example, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, cobalt blue, chromium oxide green, cobalt green, amber, synthetic iron black, etc.

[0020] The pigment (A) can be used alone or in combination of two or more.

[0021] <Micronization of Pigment> After the organic pigment has been subjected to a micronization treatment, it is preferably mixed with other raw materials. Examples of the micronization treatment method include wet grinding, dry grinding, solution precipitation method, and the like. Among these, salt milling treatment by a kneader method, which is a type of wet grinding, is preferred. The average primary particle size of the organic pigment after the micronization treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. With an appropriate particle size, the dispersibility is further improved, and the contrast ratio of the coating film is further improved. The average primary particle size is the average value of about 20 particles arbitrarily selected from the enlarged image of a TEM (transmission electron microscope). When there are a longitudinal axis length and a transverse axis length of the particle, the longitudinal axis length is used.

[0022] During the salt milling treatment, a resin can be added as necessary. Examples of the resin include natural resins, modified natural resins, synthetic resins, synthetic resins modified with natural resins, and the like. The resin is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in a water-soluble organic solvent. The amount of the resin used is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the pigment.

[0023] <Removal of Metals> When a large amount of specific metal elements are present in the colored composition as impurities other than the constituent components of the pigment, the dispersion stability over time is inhibited. In addition, the heat resistance may decrease, or the sensitivity may decrease. Further, when a color filter is produced using this, foreign matter may occur, and as a result, the brightness is likely to decrease. 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 colored composition is preferably 500 mass ppm or less.

[0024] The total amount of the specific metal elements is more preferably 300 mass ppm or less, and particularly preferably 200 mass ppm or less. Further, 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 colored composition can be obtained that can suppress costs, has excellent storage stability, and can form a color filter with less generation of foreign matter and less decrease in brightness.

[0025] The amount of each specific metal element contained in the photosensitive coloring composition is preferably 100 mass ppm or less, more preferably 50 mass ppm or less for each.

[0026] Also, metals such as Ni, Zn, Cu, Al, Fe, Fe, Co, and Co that constitute the pigment should preferably have fewer impurities that are not components of the pigment, and can be removed in the same manner as the specific metal elements by the following method. Furthermore, Mn, Cs, Ti, Co, Si, Pd, etc. may be mixed in from materials (such as catalysts) used in the manufacturing process of various raw materials of the photosensitive coloring composition, so it is preferable to remove them as much as possible.

[0027] As methods for removing the pigment (A) or metals mixed in from the equipment 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 substances with a magnet described in JP-A-2011-48736.

[0028] The content of the specific metal element can be measured by inductively coupled plasma optical emission spectrometry (ICP).

[0029] <Dye> The photosensitive coloring composition can contain a dye in addition to the pigment (A) as a colorant. 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. Also included are derivatives of the dye and lake pigments obtained by lakeifying the dye.

[0030] The dye is preferably used as a salt-forming compound. The salt-forming compounds include a salt-forming compound of an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound; a salt-forming compound of a resin component having an amino group and an acid dye or the like; a salt-forming compound of an acid dye and a compound having an onium base; a salt-forming compound of a basic dye and an organic acid, perchloric acid, or a metal salt thereof, etc. Among these, the salt-forming compound of a basic dye is preferable because of its excellent various resistances and compatibility with pigments. Note that as the compound having an onium base, a resin having a cationic group in the side chain is preferable.

[0031] 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 preferable, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferable.

[0032] <Pigment Derivative> The photosensitive coloring composition can use a dye derivative as needed. The dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Examples of the dye derivative include a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphoric acid group, and an amine salt thereof, a compound having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal, and a compound having a neutral substituent such as a phenyl group or a phthalimidoalkyl group.

[0033] The dye derivative is preferably a basic pigment derivative, and it can be used alone or in combination of two or more with other dye derivatives. As the basic pigment derivative used in the present invention, a known dye derivative having a basic group in an organic dye residue can be used. Examples thereof include a compound having a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal. Further, the basic pigment derivative shown in the present invention is a derivative having at least one basic group. Examples of the organic dye 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.

[0034] Specifically, examples of diketopyrrolopyrrole-based basic pigment derivatives include those described in JP-A-2001-220520, WO2009 / 081930 pamphlet, WO2011 / 052617 pamphlet, WO2012 / 102399 pamphlet, JP-A-2017-156397; examples of phthalocyanine-based basic pigment derivatives include those described in JP-A-2007-226161, WO2016 / 163351 pamphlet, JP-A-2017-165820, Patent No. 5753266; examples of anthraquinone-based basic pigment derivatives include those described in JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009 / 025325 pamphlet; examples of quinacridone-based basic pigment derivatives include those described in JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383; examples of dioxazine-based basic pigment derivatives include those described in JP-A-2011-162662; examples of thiazine indigo-based basic pigment derivatives include those described in JP-A-2007-314785; examples of triazine-based basic pigment derivatives include those described in JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681; examples of benzisoindole-based basic pigment derivatives include those described in JP-A-2009-57478; examples of quinophthalone-based basic pigment derivatives include those described in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-226110; examples of naphthol-based basic pigment derivatives include those described in JP-A-2012-208329, JP-A-2014-5439; examples of azo-based basic pigment derivatives include those described in JP-A-2001-172520, JP-A-2012-172092; examples of basic substituents include those described in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404, and the like. Known basic pigment derivatives are exemplified.

[0035] The content of the pigment derivative is preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass with respect to 100 parts by mass of the pigment (A).

[0036] By adding a pigment derivative to the pigment and performing a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, solvent salt milling, etc., the pigment derivative is adsorbed on the pigment surface, and the primary particles of the pigment can be made finer compared to the case where no pigment derivative is added.

[0037] <Resin (B)> The resin (B) corresponds to any one of a resin mainly having a pigment dispersion function, a resin mainly having a binder function, and a resin having both functions to approximately the same extent. As the resin (B), it contains a resin (B1) containing a blocked isocyanate group-containing structural unit and a resin (B2) containing a (meth)acryloyl group-containing vinyl polymer moiety.

[0038] <Resin (B1) containing a blocked isocyanate group-containing structural unit> As the resin (B), the resin (B1) containing a blocked isocyanate group-containing structural unit has a binder function because it is thermosetting. It is preferable that the resin (B1) further has a carboxy group-containing structural unit because it becomes a resin having an alkali-soluble binder function. The carboxy group-containing structural unit is introduced, for example, by copolymerizing (meth)acrylic acid.

[0039] (Blocked isocyanate group-containing structural unit) The block isocyanate group-containing structural unit contained in the resin (B1) having a block isocyanate group-containing structural unit is a structural unit derived from a block isocyanate group-containing monomer. The monomer is a reaction product of an isocyanate group-containing monomer and a blocking agent. In the blocking reaction, it is preferable to use an organic metal salt such as zinc or lead, or a tertiary amine or the like as a catalyst. The reaction temperature is generally about -20 to 150 °C, preferably 0 to 100 °C. Further, a solvent can be used as necessary during the reaction. Examples of the isocyanate group-containing monomer include a compound represented by the following formula (1).

[0040] Formula (1)

Chemical formula

[0041] In the above formula (1), R 1 represents a hydrogen atom or a methyl group, and R 2 represents -CO-, -COOR 3 - (wherein R 3 is an alkylene group having 1 to 6 carbon atoms) or -COO-R 4 O-CONH-R 5 - (wherein R 4 is an alkylene group having 2 to 6 carbon atoms, and R 5 is an alkylene group having 2 to 12 carbon atoms which may have a substituent or an arylene group having 6 to 12 carbon atoms). R 2 is preferably -COOR 3 -, where R 3 is preferably an alkylene group having 1 to 4 carbon atoms.

[0042] The compound represented by the above formula (1) includes, for example, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, methacryloyl isocyanate, and the like. Further, an equimolar (1 mol:1 mol) reaction product of 2-hydroxyalkyl (meth)acrylate and a diisocyanate compound can also be used. The alkyl group of the 2-hydroxyalkyl (meth)acrylate is preferably an ethyl group or an n-propyl group, more preferably an ethyl group. The diisocyanate compound includes, for example, hexamethylene diisocyanate, 2,4-(or 2,6-)toluene diisocyanate (TDI), 4,4'-diphenylmethane diisocyanate (MDI), 3,5,5-trimethyl-3-isocyanatomethylcyclohexyl isocyanate (IPDI), m-(or p-)xylene diisocyanate, 1,3-(or 1,4-)bis(isocyanatomethyl)cyclohexane, lysine diisocyanate, and the like.

[0043] Among these, 2-isocyanatoethyl (meth)acrylate, 2-isocyanatopropyl (meth)acrylate, 3-isocyanatopropyl (meth)acrylate, 2-isocyanato-1-methylethyl (meth)acrylate, 2-isocyanato-1,1-dimethylethyl (meth)acrylate, 4-isocyanatocyclohexyl (meth)acrylate, and methacryloyl isocyanate are preferred, and 2-isocyanatoethyl (meth)acrylate and 2-isocyanatopropyl (meth)acrylate are more preferred.

[0044] The blocking agents include, for example, lactam-based ones such as ε-caprolactam, δ-valerolactam, γ-butyrolactam, β-propiolactam, etc.; alcohol-based ones such as methanol, ethanol, propanol, butanol, ethylene glycol, methyl cellosolve, butyl cellosolve, methyl carbitol, benzyl alcohol, phenyl cellosolve, furfuryl alcohol, cyclohexanol, etc.; phenol-based ones such as phenol, cresol, 2,6-xylenol, 3,5-xylenol, ethylphenol, o-isopropylphenol, p-tert-butylphenol, etc., butylphenol, p-tert-octylphenol, nonylphenol, dinonylphenol, styrenated phenol, methyl 2-hydroxybenzoate, methyl 4-hydroxybenzoate, thymol, p-naphthol, p-nitrophenol, p-chlorophenol, etc.; active methylene-based ones such as dimethyl malonate, diethyl malonate, methyl acetoacetate, ethyl acetoacetate, acetylacetone, etc. Mercaptan-based ones such as butyl mercaptan, thiophenol, tert-dodecyl mercaptan, etc. Amine-based ones such as diphenylamine, phenylnaphthylamine, aniline, carbazole, etc.; acid amide-based ones such as acetanilide, acetoanisidide, acetamide, benzamide, etc. Acid imide-based ones such as succinimide, maleimide, etc. Imidazole-based ones such as imidazole, 2-methylimidazole, 2-ethylimidazole, etc. Pyrazole-based ones such as pyrazole, 3,5-dimethylpyrazole, etc. Urea-based ones such as urea, thiourea, ethylene urea, etc. Carbamate-based ones such as phenyl N-phenylcarbamate, 2-oxazolidone, etc.: imine-based ones such as ethyleneimine, polyethyleneimine, etc. Oxime-based ones such as formaldehyde oxime, acetaldehyde oxime, acetoxime, methyl ethyl ketoxime, methyl isobutyl ketoxime, cyclohexanone oxime, etc. Examples include bisulfite-based ones such as sodium bisulfite, potassium bisulfite, etc.

[0045] The blocked isocyanate group dissociates upon heating to regenerate the isocyanate group. In the present invention, the isocyanate group reacts with a reactive functional group, i.e., an acid group, and optionally included hydroxy group, amino group, etc., to form a cured product with a high crosslink density.

[0046] In this specification, the dissociation temperature of the blocking agent is preferably 80 to 150 °C.

[0047] The blocked isocyanate group-containing structural unit preferably used in the photosensitive coloring composition of the present invention is a blocked isocyanate group-containing (meth)acrylate. The blocked isocyanate group-containing (meth)acrylate preferably has a dissociation rate of the blocked isocyanate group of 5 to 99% by mass, more preferably 8 to 97% by mass, and most preferably 10 to 95% by mass when heat-treated at 100 °C for 30 minutes. The dissociation rate of the blocked isocyanate group of the blocked isocyanate group-containing (meth)acrylate is determined by preparing an n-octanol solution with a concentration of 20% by mass of the blocked isocyanate group-containing (meth)acrylate, adding dibutyltin laurate equivalent to 1% by mass and phenothiazine (polymerization inhibitor) equivalent to 3% by mass to the solution, heating at 100 °C for 30 minutes, and measuring the mass reduction ratio of the blocked isocyanate group-containing (meth)acrylate by HPLC analysis. When a blocked isocyanate group-containing (meth)acrylate with a dissociation rate within the above range is used, the stability of the copolymer during synthesis can be sufficiently ensured, the baking temperature during the production of the cured coating film can be sufficiently lowered, and the solvent resistance of the cured coating film can also be sufficiently ensured. Examples of the blocking agent for the blocked isocyanate group-containing (meth)acrylate having such a dissociation rate include γ-butyrolactam, 1-methoxy-2-propanol, 2,6-dimethylphenol, diisopropylamine, methyl ethyl ketoxime, 3,5-dimethylpyrazole, and diethyl malonate. Among these blocking agents, diethyl malonate, 3,5-dimethylpyrazole, and methyl ethyl ketoxime are more preferable from the viewpoint of low-temperature curability.

[0048] Also, it is preferable to use a blocked isocyanate group-containing (meth)acrylate in which the dissociation temperature of the blocked isocyanate group is 80°C or higher. When a blocked isocyanate group-containing (meth)acrylate having a dissociation temperature of 80°C or higher is used, the stability of the copolymer during synthesis can be sufficiently ensured, and an unintended crosslinking reaction during the modification reaction described later can be reduced. On the other hand, when the dissociation temperature of the blocked isocyanate group is 150°C or lower, the baking temperature can be sufficiently lowered and the solvent resistance of the cured coating film can also be sufficiently ensured. The dissociation temperature of the blocked isocyanate group of the blocked isocyanate group-containing (meth)acrylate is determined by preparing an n-octanol solution with a concentration of 20% by mass of the blocked isocyanate group-containing (meth)acrylate, adding dibutyltin laurate equivalent to 1% by mass and phenothiazine (polymerization inhibitor) equivalent to 3% by mass to the solution, heating at a predetermined temperature, measuring the mass reduction ratio of the blocked isocyanate group-containing (meth)acrylate after 30 minutes by HPLC analysis, and setting the temperature at which the mass reduction ratio is 80% by mass or higher as the dissociation temperature of the blocked isocyanate group.

[0049] Examples of the blocked isocyanate group-containing (meth)acrylate include KAYARAD (registered trademark) MOI-DEM represented by the following formula (2) (reaction product of methacryloyloxyethyl isocyanate and diethyl malonate, manufactured by Showa Denko K.K., dissociation temperature of blocked isocyanate group: 90 °C, dissociation rate: 90% by mass), KAYARAD MOI-BP represented by the following formula (3) (reaction product of methacryloyloxyethyl isocyanate and 3,5-dimethylpyrazole, manufactured by Showa Denko K.K., dissociation temperature of blocked isocyanate group: 110 °C, dissociation rate: 70% by mass), KAYARAD MOI-BM represented by the following formula (4) (reaction product of methacryloyloxyethyl isocyanate and methyl ethyl ketoxime, manufactured by Showa Denko K.K., dissociation temperature of blocked isocyanate group: 130 °C, dissociation rate: 18% by mass), and methacrylates corresponding thereto, and acrylates. These blocked isocyanate group-containing (meth)acrylates may be used alone or in combination of two or more.

[0050]

Chemical formula

[0051] Formula (4)

Chemical formula

[0052] The resin (B1) containing a blocked isocyanate group-containing structural unit may be, for example, a resin having a dispersion function described in JP-A-2009-155406. The resin (B1) containing a blocked isocyanate group-containing structural unit can have monomer units derived from the following other monomers.

[0053] Other monomers include, for example, (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate; or (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, or acryloylmorpholine; styrenes such as styrene or α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; oxetane group-containing (meth)acrylates such as (3-methyl-3-oxetanyl)methyl (meth)acrylate, (3-ethyl-3-oxetanyl)methyl (meth)acrylate, (3-butyl-3-oxetanyl)methyl (meth)acrylate, or (3-hexylthiol-3-oxetanyl)methyl (meth)acrylate; fatty acid vinyls such as vinyl acetate or vinyl propionate, etc.

[0054] The proportion of the block isocyanate group-containing structural unit is preferably 1 to 40 mol%, more preferably 2 to 30 mol%, and even more preferably 3 to 25 mol% in all the structural units of the resin (B1). When the proportion of the block isocyanate group-containing structural unit is 1 to 40 mol%, the crosslinking density of the cured coating film increases and the solvent resistance improves. Also, the storage stability of the resin (B1) does not decrease.

[0055] <Resin (B2) containing a (meth)acryloyl group-containing vinyl polymer moiety> The resin (B2) containing a (meth)acryloyl group-containing vinyl polymer moiety is a resin having both a binder function and dispersibility. The vinyl polymer moiety serves as a steric repulsion site to enhance dispersibility, and the (meth)acryloyl group acts as a photocrosslinking site.

[0056] It is more preferable that the resin (B2) is further a resin having an aromatic carboxylic acid moiety. The aromatic carboxylic acid moiety has a high affinity for the pigment surface. Therefore, since the resin (B2) efficiently wraps the pigment, the exposed surface of the pigment is suppressed, and it becomes difficult for the substrate and the pigment to come into direct contact, improving the adhesion.

[0057] The aromatic carboxylic acid moiety is derived from one or more acid anhydrides selected from, for example, tetracarboxylic acid anhydrides or tricarboxylic acid anhydrides.

[0058] A resin having an aromatic carboxylic acid moiety derived from a tetracarboxylic acid anhydride can be synthesized, for example, by adding a tetracarboxylic acid anhydride to the hydroxyl groups in a vinyl polymer having two hydroxyl groups at one end. Examples of the tetracarboxylic acid anhydride, which is a raw material for a comb-shaped resin-type dispersant, and the raw material for the vinyl polymer, which is a part of the structure, include resins described in International Publication No. WO2008 / 007776.

[0059] These can be used alone or in combination. Those preferably used in the present invention are aromatic tetracarboxylic dianhydrides from the viewpoint of reducing the viscosity of the photosensitive coloring composition. For example, pyromellitic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, ethylene glycol dianhydride trimellitate ester, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 3,3',4,4'-biphenyl sulfone tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride, and 3,3',4,4'-biphenyl tetracarboxylic dianhydride are preferred. Among these, pyromellitic anhydride is preferred.

[0060] Resins having an aromatic carboxylic acid moiety derived from tricarboxylic dianhydride can, for example, synthesize a linear resin-type dispersant having a carboxyl group by adding the hydroxyl groups in a vinyl polymer having two hydroxyl groups at one end to tricarboxylic dianhydride. For example, the compounds described in JP-A-2009-251481, JP-A-2007-23195, and JP-A-1996-143651 can be mentioned.

[0061] Examples of tricarboxylic dianhydride include benzenetricarboxylic dianhydride (1,2,3-benzenetricarboxylic dianhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic dianhydride], etc.), naphthalenetricarboxylic dianhydride (1,2,4-naphthalenetricarboxylic dianhydride, 1,4,5-naphthalenetricarboxylic dianhydride, 2,3,6-naphthalenetricarboxylic dianhydride, 1,2,8-naphthalenetricarboxylic dianhydride, etc.), 3,4,4'-benzophenone tricarboxylic dianhydride, 3,4,4'-biphenyl ether tricarboxylic dianhydride, 3,4,4'-biphenyl tricarboxylic dianhydride, 2,3,2'-biphenyl tricarboxylic dianhydride, 3,4,4'-biphenylmethane tricarboxylic dianhydride, 3,4,4'-biphenyl sulfone tricarboxylic dianhydride, etc. Among these, trimellitic anhydride is preferred.

[0062] The weight average molecular weight of the vinyl polymer part of the resin (B2) is preferably from 500 to 30,000, more preferably from 5,000 to 20,000, and even more preferably from 7,000 to 10,000.

[0063] The number average molecular weight of the vinyl polymer part of the resin (B2) is preferably from 2,000 to 6,000.

[0064] The photosensitive coloring composition contains a resin (B1) containing a block isocyanate group-containing structural unit and a resin (B2) containing a (meth)acryloyl group-containing vinyl polymer part. The reason is that when trying to obtain sufficient chemical resistance with a resin (B2) containing a vinyl polymer part having a (meth)acryloyl group, photocuring becomes excessive, the line width of the pattern after development becomes thick, and the resolution decreases, making it difficult to form a fine pattern. However, by combining with a resin (B1) containing a block isocyanate group-containing structural unit, while maintaining appropriate photocurability, desired curability can be obtained even in a low-temperature heating process of 150°C or lower, so the chemical resistance is improved. Therefore, the photosensitive coloring composition has improved chemical resistance, low-temperature curability, and fine pattern formation.

[0065] The total amount of the resin (B1) and the resin (B2) is preferably 80% by mass or more in the total amount of the resin (B).

[0066] The acid value of the resin (B1) containing a block isocyanate group-containing structural unit and the resin (B2) containing a vinyl polymer part having a (meth)acryloyl group is preferably from 10 to 250 mgKOH / g in terms of nonvolatile content, more preferably from 40 to 200 mgKOH / g, and even more preferably from 50 to 160 mgKOH / g. Appropriate acid value improves storage stability.

[0067] <Other resins> Examples of the resins that can be used in combination with the resin (B1) and the resin (B2) as other resins include resins having a dispersion function and resins having a binder function. Examples of the resin having a dispersing function include resins described in, for example, WO2008 / 007776, JP-A-2008-029901, JP-A-2009-155406, JP-A-2010-185934, JP-A-2011-157416, JP-A-2009-251481, JP-A-2007-23195, JP-A-1996-143651, JP-A-2007-140487, etc.

[0068] The resin having the binder function is preferably a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm when a film having a thickness of 2 μm is formed. Note that the transmittance is preferably 95% or more. The resin having the binder function is preferably a thermoplastic resin or a photosensitive resin. Further, the resin having the binder function preferably has alkali solubility. Thereby, the film formed from the photosensitive coloring composition can be patterned by photolithography. The photosensitive resin having no alkali solubility and the alkali-soluble resin can have a thermosetting group. Examples of the thermosetting group include an epoxy group and an oxetanyl group.

[0069] The resin having the binder function can be used alone or in combination of two or more.

[0070] The content of the resin having the binder function is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on 100 parts by mass of the pigment (A). When contained in an appropriate amount, a film can be easily formed and good color characteristics are easily obtained.

[0071] Examples of the alkali-soluble resin include resins having acidic groups such as carboxyl groups and sulfone groups. Examples of the alkali-soluble thermoplastic resin include acrylic resins having acidic groups, α-olefin / (meth)maleic anhydride copolymers, styrene / styrene sulfonic acid copolymers, ethylene / (meth)acrylic acid copolymers, or isobutylene / (meth)maleic anhydride 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.

[0072] <Thermoplastic resin> The thermoplastic resin does not have alkali solubility. 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.

[0073] <Alkali-soluble photosensitive resin> The alkali-soluble photosensitive resin has photosensitivity because it has a polymerizable unsaturated group. The alkali-soluble photosensitive resin has alkali solubility and only needs to have photosensitivity, and known resins can be used. Resins synthesized by the following method (i) or (ii) are preferred. When the alkali-soluble photosensitive resin is used, three-dimensional crosslinking occurs upon light irradiation, increasing the crosslinking density and thus improving the chemical resistance of the film.

[0074] [Method (i)] In method (i), for example, first, a polymer of an epoxy group-containing monomer and other monomers is synthesized. Next, a monocarboxyl 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 photosensitive resin. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

[0075] 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 preferred from the viewpoint of reactivity.

[0076] The monocarboxyl group-containing monomer includes, for example, monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl, alkoxyl, halogen, nitro, cyano-substituted products of (meth)acrylic acid, etc.

[0077] Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. The polybasic acid anhydride may have a carboxyl group that does not form an acid anhydride.

[0078] Examples of the other monomers include (meth)acrylates such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate, or (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, or acryloylmorpholine, styrenes such as styrene or α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate or vinyl propionate.

[0079] In addition, N-substituted maleimides such as cyclohexyl maleimide, phenyl maleimide, methyl maleimide, ethyl maleimide, 1,2-bismaleimide ethane, 1,6-bismaleimide hexane, 3-maleimide propionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimide diphenylmethane, bis(3-ethyl-5-methyl-4-maleimide phenyl)methane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzyl maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimide benzoate, N-succinimidyl-3-maleimide propionate, N-succinimidyl-4-maleimide butyrate, N-succinimidyl-6-maleimide hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimide acridine, etc., EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, EO or propylene oxide (PO)-modified (meth)acrylate of p-cumylphenol, EO-modified (meth)acrylate of nonylphenol, PO-modified (meth)acrylate of nonylphenol, etc. can be mentioned.

[0080] Method (ii) includes, for example, synthesizing a hydroxyl group-containing monomer, a carboxyl group-containing monomer, and other monomers to produce a polymer. Then, a method of synthesizing an alkali-soluble photosensitive resin by reacting the isocyanate group of an isocyanate group-containing monomer with the hydroxyl group of the polymer can be mentioned.

[0081] The hydroxyl group-containing monomer includes, for example, hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2- or 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, or cyclohexanedimethanol mono(meth)acrylate. Also included are polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide, etc. to hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylates obtained by adding polyγ-butyrolactone, polyε-caprolactone, and / or poly12-hydroxystearic acid, etc. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred, and glycerol mono(meth)acrylate is more preferred.

[0082] The isocyanate group-containing monomer includes, for example, 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, or 1,1-bis[methacryloyloxy]ethyl isocyanate, etc.

[0083] In addition to the other monomers exemplified in the above method (i), monomers that can be used other than the above monomers include phosphate group-containing monomers, etc.

[0084] The phosphate group-containing monomer is, for example, a compound obtained by reacting a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid with the hydroxyl group of a hydroxyl group-containing monomer.

[0085] The above raw materials of the resin having a binder function can be used alone or in combination of two or more. Also, the resin having a binder function can be used alone or in combination of two or more.

[0086] <Thermosetting compound> The photosensitive coloring composition can contain a thermosetting compound. When producing a color filter using the photosensitive coloring composition, the thermosetting compound thermosets in the post-baking process to increase the crosslink density of the film and improve the heat resistance. Thereby, pigment aggregation in the post-baking process is suppressed and the contrast ratio is improved.

[0087] The thermosetting compound may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound include an epoxy compound, an oxetane compound, a benzoguanamine compound, a rosin-modified maleic acid compound, a rosin-modified fumaric acid compound, a melamine compound, a urea compound, and a phenol compound. Among these, an epoxy compound and an oxetane compound are preferred.

[0088] Epoxy compounds include, for example, polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenols, aromatic-substituted phenols, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehydes, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polymers of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.), polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzene dimethanol, α,α,α’,α’-benzene dimethanol, biphenyl dimethanol, α,α,α’,α’-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α’-dichloroxylene, bischloromethyl biphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether-based epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine-based epoxy resins, glycidyl ester-based epoxy resins, and the like.

[0089] (Oxetane compound) An oxetane compound is a compound having an oxetane group. Oxetane compounds include monofunctional oxetane compounds, difunctional oxetane compounds, and trifunctional or higher oxetane compounds.

[0090] Examples of the functional oxetane compound include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane and the like.

[0091] The difunctional oxetane compounds include, for example, 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether-3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl)ether, triethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, tetraethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, 1,4-bis(3-ethyl-3-oxetanylmethoxy)butane, 1,6-bis(3-ethyl-3-oxetanylmethoxy)hexane, polyethylene glycol bis(3-ethyl-3-oxetanylmethyl)ether, ethylene oxide (EO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, propylene oxide (PO)-modified bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, PO-modified hydrogenated bisphenol A bis(3-ethyl-3-oxetanylmethyl)ether, EO-modified bisphenol F (3-ethyl-3-oxetanylmethyl)ether, and the like.

[0092] Examples of those having a trifunctional or higher oxetane group include pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa(3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis(3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis(3-ethyl-3-oxetanylmethyl) ether, resins containing an oxetane group (for example, oxetane-modified phenol novolak resins described in Japanese Patent No. 3783462, etc.), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the aforementioned OXE-30.

[0093] The content of the thermosetting compound is preferably 0.5 to 50 parts by mass, more preferably 1 to 40 parts by mass. When it contains an appropriate amount, the solvent resistance of the film is further improved.

[0094] (Basic resin type dispersant) The photosensitive coloring composition can contain a basic resin type dispersant. Examples of the basic resin type dispersant include nitrogen atom-containing graft copolymers, nitrogen atom-containing acrylic block copolymers having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, etc. in the side chain, and urethane-based polymer dispersants.

[0095] The number average molecular weight of the basic resin type dispersant used in the present invention is usually preferably 500 to 50,000, particularly preferably 3,000 to 30,000. When the above number average molecular weight is less than 500, the effects of steric repulsion by the pigment affinity group, the compatibility effect with the pigment carrier, and the compatibility effect with the pigment carrier and the solvent when using a solvent are small, making it difficult to prevent pigment aggregation, and the viscosity of the dispersion may increase. Also, when the number average molecular weight is 50,000 or more, the amount of resin required for dispersion increases, which may lead to a decrease in the pigment concentration in the coating film.

[0096] The amine value of the basic resin type dispersant is preferably 35 to 100 mgKOH / g. More preferably, it is 50 to 75 mgKOH / g. When the amine value is less than 35 mgKOH / g, it may not be sufficiently adsorbed to the pigment and may result in poor dispersion. When it exceeds 100 mgKOH / g, the adsorption efficiency to the pigment may deteriorate due to adsorption or reaction with acidic components in the pigment carrier, resulting in poor dispersion.

[0097] For the basic resin type dispersant, various types of resin systems such as vinyl, urethane, polyester, polyether, or polyamide can be used. However, a vinyl monomer copolymer type with easy resin design and excellent various resistances is preferred. Specifically, a copolymer resin of an N,N-disubstituted amino group-containing vinyl monomer unit, an alkyl (meth)acrylate monomer unit, and other vinyl monomer units is suitable.

[0098] Examples of the N,N-disubstituted amino group-containing vinyl monomer unit include N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N,N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate, N,N-dimethylaminoethyl (meth)acrylamide, or N,N-diethylaminoethyl (meth)acrylamide, etc., but are not necessarily limited thereto. These monomer units adsorb to the pigment as basic group-containing monomer units.

[0099] Examples of the alkyl (meth) acrylate monomer units include (meth)acrylic esters obtained by the reaction of unsaturated monocarboxylic acids such as methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, or lauryl (meth)acrylate with alkyl alcohols having 1 to 18 carbon atoms, but are not necessarily limited thereto. These monomer units act as pigment carrier affinity groups.

[0100] Examples of other vinyl monomer units include nitro group-containing vinyl monomers such as (meth)acrylonitrile, vinyl aromatic monomers such as styrene, α-methylstyrene, or benzyl (meth)acrylate, hydroxyl group-containing vinyl monomers such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, or polyethylene glycol (meth)acrylate, amide group-containing vinyl monomers such as (meth)acrylamide, N,N-dimethylacrylamide, N-isopropylacrylamide, or diacetoneacrylamide, vinyl monomers such as N-methylol (meth)acrylamide or dimethylol (meth)acrylamide, alkoxymethyl group-containing vinyl monomers such as N-methoxymethyl (meth)acrylamide or N-butoxymethyl (meth)acrylamide, olefins such as ethylene, propylene, or isoprene, dienes such as chloroprene or butadiene, vinyl ethers such as methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, fatty acid vinyls such as vinyl acetate or vinyl propionate, etc. These are used as appropriate according to the purpose, but are not necessarily limited thereto.

[0101] Examples of the basic resin type dispersant having a comb-shaped basic substituent obtained by modifying a polymer having a primary amino group-containing monomer unit such as allylamine, or polyethyleneimine, polyethylene polyamine, polyxylylene poly(hydroxypropylene) polyamine, or poly(aminomethylated) epoxy resin, etc. with a polyester resin, acrylic resin, or polyether resin, etc. can also be mentioned.

[0102] Examples of commercially available products of such basic resin type dispersants include DISPERBYK 161, 162, 163, 164, 166, 167, 168, 174, 182, 183, 184, 185, 2000, 2001, 2050, 2150, 2163, 2164, BYK-LPN6919, 21116 manufactured by BYK-Chemie Japan Co., Ltd., SOLSPERSE 11200, 13240, 13650, 13940, 24000, 26000, 28000, 32000, 32500, 32550, 32600, 33000, 34750, 35100, 35200, 37500, 38500, 39000, 53095, 56000, 71000 manufactured by Lubrizol Japan Ltd., EFKA 4300, 4330, 4046, 4060, 4080 manufactured by BASF, and Ajisper PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Inc., etc.

[0103] The content of the basic resin type dispersant is preferably about 3 to 200% by mass, more preferably about 5 to 100% by mass, based on the pigment (A). When contained in an appropriate amount, the film-forming property is further improved.

[0104] Also, as disclosed in JP-A-2009-185277, a preferred example is to use in combination a resin type dispersant having an aromatic carboxyl group and a vinyl resin having a tertiary amino group (having the function of a resin type dispersant).

[0105] <Polymerizable compound (D)> The polymerizable compound (D) is a monomer or oligomer containing a polymerizable unsaturated group. The polymerizable compound (D) contributes to the formation of a film of the photosensitive coloring composition. Examples of the polymerizable compound (D) include acid group-containing monomers, urethane bond-containing monomers, and other monomers. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)acryloyl group, a (meth)allyl group, etc. Note that an oligomer is a compound having a molecular weight of 1000 or more.

[0106] Examples of the acid group of the acid group-containing monomer include a sulfonic acid group, a carboxyl group, a phosphoric acid group, etc.

[0107] Examples of the acid group-containing monomer include esterified products of polyhydric alcohols and free hydroxyl group-containing poly(meth)acrylates with (meth)acrylic acid and dicarboxylic acids; esterified products of polycarboxylic acids and monohydroxyalkyl (meth)acrylates, etc. Specific examples include free carboxyl group-containing monoesterified products of monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, dipentaerythritol pentamethacrylate, etc. and dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, phthalic acid, etc.; free carboxyl group-containing oligoesterified products of tricarboxylic acids such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, etc. and monohydroxymonoacrylates or monohydroxymonomethacrylates such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, 2-hydroxypropyl methacrylate, etc.

[0108] (Urethane bond-containing monomer) The urethane bond-containing monomer includes, for example, polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, polyfunctional urethane acrylate obtained by reacting an alcohol with a polyfunctional isocyanate and then reacting with a (meth)acrylate having a hydroxyl group, and the like.

[0109] The (meth)acrylate having a hydroxyl group includes 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, reaction product of an epoxy group-containing compound and a carboxy (meth)acrylate, hydroxyl group-containing polyol polyacrylate, and the like.

[0110] The polyfunctional isocyanate includes tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethane diisocyanate, isophorone diisocyanate, polyisocyanate, and the like.

[0111] Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, 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 acrylic esters and methacrylic 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, etc.

[0112] The polymerizable compound (D) can be used alone or in combination of two or more.

[0113] The blending amount of the coincidence compound (D) 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.

[0114] <Photoinitiator (C)> The photoinitiator (C) is, for example, an acetophenone-based compound such as 4-phenoxydichloroacetophenone, 4-t-butyldichloroacetophenone, 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; a benzoin-based compound such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; a benzophenone-based compound such as benzophenone, benzoyl benzoic acid, methyl benzoyl benzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; a thioxanthone-based compound such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; a triazine-based compound 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;Oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl]-, 2-(O-benzoyloxime), or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-, 1-(O-acetyloxime); phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, or ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds, etc. Among these, oxime ester compounds are preferred.;

[0115] The photopolymerization initiator (C) can be used alone or in combination of two or more kinds.;

[0116] (Oxime ester compound) The oxime ester compound absorbs ultraviolet rays, causing cleavage of the N-O bond of the oxime and generating iminyl radicals and alkyloxy radicals. These radicals further decompose to generate highly active radicals, so that a pattern can be formed with a small exposure amount. When the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the degree of curing of the coating film may be low. However, since the oxime ester compound has a high quantum efficiency, it is preferably used.;

[0117] Examples of the oxime ester compound include oxime ester-based photopolymerization initiators described in JP-A No. 2007-210991, JP-A No. 2009-179619, JP-A No. 2010-037223, JP-A No. 2010-215575, JP-A No. 2011-020998, etc.;

[0118] The content of the photopolymerization initiator (C) is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass, per 100 parts by mass of the pigment (A). When blended in an appropriate amount, the photocurability and developability are further improved.;

[0119] <Sensitizer> The photosensitive coloring composition may further contain a sensitizer. Examples of the sensitizer include unsaturated ketones typified by chalcone derivatives, dibenzalacetone, etc., 1,2-diketone derivatives typified by benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, polymethine dyes such as cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyllin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organoruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acylphosphine oxides, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'-tetra(t-butylperoxycarbonyl)benzophenone, 4,4'-bis(diethylamino)benzophenone, etc. Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferable. Specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole, etc. are more preferable.

[0120] The sensitizer can be used alone or in combination of two or more.

[0121] The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the polymerization initiator (D). When contained in an appropriate amount, the photocurability and developability are further improved.

[0122] The content of the sensitizer is preferably 3 to 60 parts by mass, more preferably 5 to 50 parts by mass, based on 100 parts by mass of the photopolymerization initiator (C). When contained in an appropriate amount, the curability and developability are further improved.

[0123] <Thiol-based chain transfer agent> The photosensitive coloring composition can contain a chain transfer agent. The chain transfer agent is preferably a thiol-based chain transfer agent. When the thiol-based chain transfer agent is used in combination with a photopolymerization initiator, thiyl radicals that are less susceptible to polymerization inhibition by oxygen are generated during radical polymerization after light irradiation, and the sensitivity of the photosensitive coloring composition is improved. The thiol-based chain transfer agent can be classified into monofunctional thiols having one thiol group and polyfunctional thiols having two or more thiol groups.

[0124] Monofunctional thiols include, for example, 1-hexanethiol, 1-octanethiol, 2-ethylhexyl 3-mercaptopropionate, 3-methoxybutyl 3-mercaptopropionate, tridecyl 3-mercaptopropionate, 2-methyl-1-butanethiol, 2-methyl-2-butanethiol, aryl mercaptan, cyclohexyl mercaptan, thiophenol, phenethyl mercaptan, 2-ethylthiophenol, 4-methoxybenzothiophenol, 2-naphthalenethiol, mercaptoimidazole, mercaptooxazole, mercaptothiazole, mercaptotriazole, mercaptothiadiazole, mercaptooxadiazole, mercaptobenzimidazole, mercaptobenzoxazole, mercaptobenzothiazole, and their derivatives, etc.

[0125] Polyfunctional thiols include, for example, 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., and preferably, ethylene glycol bisthiopropionate, trimethylolpropane tristthiopropionate, pentaerythritol tetrakisthiopropionate.

[0126] In the exposure process of the pattern formation process, the exposure of the portion in contact with the substrate deep within the film may be insufficient compared to the surface layer portion, and the portion in contact with the substrate after development may become thinner. Conventionally, in response to this problem, a polyfunctional thiol compound is often used as a chain transfer agent that moves radicals generated in the surface layer portion to the deep portion of the film. However, by using a monofunctional thiol compound, the occurrence of thinning of the portion in contact with the substrate after development can be more effectively suppressed, and it becomes possible to form a finer pattern with higher rectangularity.

[0127] The thiol-based chain transfer agent can be used alone or in combination of two or more kinds.

[0128] The content of the thiol-based chain transfer agent is preferably 30 to 200 parts by mass, more preferably 50 to 150 parts by mass, based on 100 parts by mass of the photopolymerization initiator (C). Further, in 100 mass% of the nonvolatile content of the photosensitive coloring composition, 0.1 to 10 mass% is preferable, and 0.1 to 5 mass% is more preferable. 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.

[0129] <Polymerization inhibitor> The photosensitive coloring composition can contain a polymerization inhibitor. Thereby, since the photosensitivity due to the diffracted light of the mask can be suppressed during the exposure of the photolithography method, it becomes easier to obtain a pattern with a desired shape.

[0130] Examples of the polymerization inhibitor include alkylcatechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert-butylcatechol, 3,5-di-tert-butylcatechol; alkylresorcinol 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 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.

[0131] 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.

[0132] <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.

[0133] The content of the ultraviolet absorber is preferably 5 to 70% by mass in a total of 100% by mass of the photopolymerization initiator and the ultraviolet absorber. When contained in an appropriate amount, the developability after development is further improved.

[0134] Also, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass in 100% by mass of the non-volatile content of the photosensitive coloring composition. When contained in an appropriate amount, the adhesion between the substrate and the film is further improved, and good developability is obtained.

[0135] 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.

[0136] 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.

[0137] 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.

[0138] Salicylic acid ester compounds include, for example, phenyl salicylate, p-octylphenyl salicylate, p-tert-butylphenyl salicylate, and the like.

[0139] <Antioxidant> The photosensitive coloring composition can contain an antioxidant. The antioxidant can prevent the film formed from the photosensitive coloring composition from yellowing due to oxidation during heat curing or heat treatment during ITO annealing, and can suppress a decrease in the transmittance of the film. In particular, when the pigment concentration of the photosensitive coloring composition is high, since the content of the polymerizable compound (D) relatively decreases, if it is dealt with by increasing the amount of the photoinitiator or blending a thermosetting compound, the film is likely to yellow. Therefore, by including an antioxidant, yellowing due to oxidation during the heating process can be prevented, and a decrease in the transmittance of the film can be suppressed.

[0140] The antioxidant is a compound having a radical scavenging function or a peroxide decomposing function. Examples of the antioxidant include hindered phenol compounds, hindered amine compounds, phosphorus compounds, sulfur compounds, hydroxylamine compounds, and the like. Note that the antioxidant is preferably a compound that does not contain a halogen atom.

[0141] Among these, from the viewpoint of achieving both the transmittance and sensitivity of the coating film, hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferable.

[0142] The antioxidant can be used alone or in combination of two or more.

[0143] The content of the antioxidant is preferably 0.5 to 5.0% by mass in 100% by mass of the nonvolatile content of the photosensitive coloring composition. Thereby, the transmittance, spectral characteristics, and sensitivity are further improved.

[0144] <Leveling agent> The photosensitive coloring composition can contain a leveling agent. Thereby, the wettability with respect to the transparent substrate during film formation and the drying property of the film are further improved. Examples of the leveling agent include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and the like.

[0145] The content of the leveling agent is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass in the non-volatile content of the photosensitive coloring composition. Within this range, the balance of the coatability, pattern adhesion, and transmittance of the photosensitive coloring composition is further improved.

[0146] <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.

[0147] 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).

[0148] <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, and 3-acryloxypropyltrimethoxysilane; epoxy silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; amino silanes 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, and the hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; mercapto silanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryl silanes such as p-styryltrimethoxysilane; ureido silanes such as 3-ureidopropyltriethoxysilane; sulfide silanes such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanate silanes such as 3-isocyanatopropyltriethoxysilane.

[0149] 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 pigment (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.

[0150] <Solvent> The photosensitive coloring composition can contain a solvent. As a result, the viscosity of the photosensitive coloring composition can be easily adjusted, and it is easy to form a film with a smooth surface. The solvent can be appropriately selected according to the purpose of use and can be contained in an appropriate amount.

[0151] Examples of the solvent include ester solvents (solvents containing -COO- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -COO-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO-, and -COO-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0152] Among these, solvents having a boiling point at 1 atm of 120°C or higher and 180°C or lower are preferred in terms of coatability and drying properties. For example, propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, N,N-dimethylformamide, N-methylpyrrolidone, etc. are more preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, etc. are even more preferred.

[0153] The solvent can be used alone or in combination of two or more.

[0154] <Manufacture of Photosensitive Coloring Composition> For example, the photosensitive coloring composition is prepared by performing a dispersion treatment using a pigment (A), a resin-type dispersant, a solvent, etc. to prepare a pigment dispersion. Next, the pigment dispersion, a resin having a binder function, a polymerizable compound (D), and a photopolymerization initiator (C) can be mixed. The timing of blending each material is arbitrary. Also, the dispersion step can be performed multiple times.

[0155] For the dispersion treatment, for example, dispersion apparatuses such as a kneader, a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, or an attritor can be used.

[0156] <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 centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or a membrane filter, etc. Thus, it is preferable that the photosensitive colored composition substantially does not contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

[0157] <Water Content in Photosensitive Colored Composition> The photosensitive colored composition of the present invention preferably has a water content of 2% by mass or less in the photosensitive colored composition.

[0158] With the above water content, the photosensitive colored composition is excellent in dispersion stability and sensitivity even after storage over time.

[0159] Note that the water content in the photosensitive colored composition is preferably 1.8% by mass or less, more preferably 1.6% by mass or less. With a sufficiently small water content within this range, problems are less likely to occur in dispersion stability and sensitivity even after storage over time.

[0160] The method for controlling the water content is not particularly limited, and known methods can be used. For example, methods such as a method of producing the photosensitive colored composition while blowing in a dried inert gas, or a method of adding molecular sieves for dehydration after production can be mentioned. Among them, a method of producing while blowing in a dried inert gas is preferable.

[0161] The water content can be measured by a known method such as the Karl Fischer method.

[0162] <Amount of Toluene in Photosensitive Coloring Composition> The photosensitive coloring composition of the present invention can contain toluene. The content of toluene is preferably 0.1 to 10 mass ppm in the photosensitive coloring composition. The upper limit of the content of toluene is preferably 9 mass ppm or less, more preferably 8 mass ppm or less, and even more preferably 7 mass ppm or less. The lower limit is preferably 0.2 mass ppm or more, more preferably 0.3 mass ppm or more, and even more preferably 0.4 mass ppm or more.

[0163] <Cured Film, Which is a Cured Product of Photosensitive Coloring Composition> The cured film, which is a cured product of the photosensitive coloring composition, means a filter segment, and its formation can be produced by, for example, printing method, electrodeposition method, transfer method, inkjet method, photolithography method, etc. In this specification, the most preferred photolithography method will be described.

[0164] In the photolithography method, for example, a photosensitive coloring composition containing a colorant of a certain color tone is applied onto a transparent substrate so that the dry film thickness becomes about 0.2 to 5 μm to form a film. The obtained film (hereinafter referred to as the first film) is exposed (light irradiation: exposure step) through a mask having a predetermined pattern. Next, development is carried out by immersing it in a solvent or an alkaline developer or spraying the developer such as by spraying to remove the uncured portion to obtain a desired pattern. By performing this process in the same manner using a photosensitive coloring composition having a colorant of another color tone, filter segments of each color can be manufactured. Further, a second film (oxygen barrier film) can be formed on the first film before exposure using polyvinyl alcohol or a water-soluble acrylic resin. Thereby, since the first film does not come into contact with oxygen, the exposure sensitivity is further improved. Also, the color filter can be heated to cure the uncured photopolymerizable compound in the filter segment.

[0165] Examples of the coating device include spray coating, spin coating, slit coating, roll coating, etc. A drying process can be performed during coating. Examples of the drying device include a hot air oven, an infrared heater, etc.

[0166] In the exposure process, 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 the exposure, ultraviolet rays such as g-line, h-line, i-line, etc. are preferably used.

[0167] Examples of the developer as an alkaline developer include inorganic alkalis such as sodium carbonate and sodium hydroxide; and organic alkalis such as dimethylbenzylamine and triethanolamine. Further, an antifoaming agent and a surfactant can be added to the developer.

[0168] <Color Filter> The color filter in this specification has filter segments formed from a photosensitive coloring composition. Also, the color filter preferably has a substrate (also referred to as a transparent substrate). The filter segments preferably have a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of the pigment (A) to be used. Further, the filter segments can have a magenta filter segment, a cyan filter segment, and a yellow filter segment instead of these. Note that a reflective substrate can be used instead of the transparent substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[0169] <Method for Manufacturing a Color Filter> For the color filter, it is preferable to first form a black matrix on the substrate and then form the filter segments. Note that a thin film transistor (TFT) can be formed in advance on the substrate and then the black matrix can be formed. Examples of the black matrix include inorganic films such as chromium, a multilayer film of chromium / chromium oxide, titanium nitride, etc., and a resin film in which a light-shielding agent is dispersed.

[0170] The color filter of the present invention is bonded to a counter substrate using a sealant, liquid crystal is injected from an injection port provided in the seal portion, and then the injection port is sealed. If necessary, a polarizing film or a retardation film is bonded to the outside of the substrate to manufacture a color liquid crystal display device. This color liquid crystal display device can be used in a liquid crystal display mode that performs colorization using a color filter such as twisted nematic (TN), super twisted nematic (STN), in-plane switching (IPS), vertical alignment (VA), optically compensated bend (OCB), etc.

[0171] In this specification, the color filter can be used for applications such as solid-state imaging devices, organic EL display devices, quantum dot display devices, electronic paper, and head-mounted displays in addition to liquid crystal display devices.

[0172] <Solid-state imaging device> The solid-state imaging device of the present invention includes the above-described color filter of the present invention. The solid-state imaging device is not particularly limited, and examples of its configuration include the following.

[0173] On a support, it has a plurality of photodiodes constituting the light-receiving area of the solid-state imaging device and a transfer electrode made of polysilicon or the like. On the photodiodes and the transfer electrode, it has a light-shielding film made of tungsten or the like with an opening only in the light-receiving portion of the photodiodes. On the light-shielding film, it has a device protection film made of silicon nitride or the like formed so as to cover the entire surface of the light-shielding film and the light-receiving portion of the photodiodes. On the device protection film, it has a configuration having the cured film of the present invention. Furthermore, it may have a configuration having a condensing means (for example, a microlens, etc. The same applies hereinafter) on the device protection film and under (closer to the support) the cured film of the present invention, or a configuration having a condensing means on the cured film of the present invention. Also, in the solid-state imaging device, the color filter may have a structure in which a cured film forming each color pixel is embedded in a space partitioned, for example, in a lattice shape by a partition wall. In this case, the partition wall is preferably of a low refractive index with respect to each color pixel.

[0174] <Liquid crystal display device> The liquid crystal display device of the present invention includes a color filter. The liquid crystal display device of the present invention 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.

[0175] Examples of the white LED light source include those in which a fluorescent filter is formed on the surface of a blue LED and those in which a phosphor is contained in the resin package of a blue LED. It has a wavelength (λ3) at which the emission intensity is maximized within the range of 430 nm to 485 nm, a wavelength (λ4) at which the emission intensity is maximized within the range of 530 nm to 580 nm, and a wavelength (λ5) at which the emission intensity is maximized within the range of 600 nm to 650 nm. And a white LED light source (LED1) having a spectral characteristic in which 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, or a white LED light source (LED2) having a spectral characteristic in which it has a wavelength (λ1) at which the emission intensity is maximized within the range of 430 nm to 485 nm, a second peak wavelength (λ2) of the 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 is 0.2 or more and 0.7 or less is preferable.

[0176] Examples of LED1 include NSSW306D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.), NSSW304D-HG-V1 (manufactured by Nichia Chemical Industries, Ltd.), etc.

[0177] Examples of LED2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.), NSSW304D (manufactured by Nichia Chemical Industries, Ltd.), etc.

Example

[0178] Hereinafter, the present invention will be described by way of examples. Needless to say, the present invention is not limited to the examples. "Parts" in the examples represent "parts by mass", and "%" represents "% by mass". Note that Examples 25 to 27 and Examples 39 to 41 are reference examples.

[0179] 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.

[0180] <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 major axis diameter of the primary particles of each pigment were measured, and the average was taken as the particle size of the pigment particles. Next, for more than 100 pigment particles, the volume (weight) of each particle was approximated by a rectangular parallelepiped with the obtained particle size, and the volume average particle size was taken as the average primary particle diameter.

[0181] (Measurement of dispersed particle diameter) Using Microtrac UPA-EX150 manufactured by Nikkiso Co., Ltd. which 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. As the dilution solvent for measurement, the solvents used in the dispersion were respectively used, and the measurement was performed immediately after sample adjustment for the samples treated with ultrasonic waves.

[0182] (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 pairs and used. The oven temperature was 40 ° C, a THF solution was used as the eluent, and the measurement was performed at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent composed of the above-mentioned eluent at 1 wt%, and 20 microliters were injected. All molecular weights are values in terms of polystyrene conversion.

[0183] (Acid value of resin) To 0.5 - 1 g of the resin solution, 80 ml of acetone and 10 ml of water were added, stirred, and uniformly dissolved. Using a 0.1 mol / L aqueous KOH solution as the titrant, titration was performed using an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd., model "COM - 555") to measure the acid value (mgKOH / g) of the resin solution. Then, the acid value per non - volatile content of the resin was calculated from the acid value of the resin solution and the non - volatile content concentration of the resin solution.

[0184] (Amine value (mgKOH / g) of the basic resin type dispersant) The amine value of the basic resin type dispersant is the value obtained by converting the total measured amine value (mgKOH / g) to non - volatile content basis in accordance with the method of ASTM D 2074.

[0185] (Ammonium salt value (mgKOH / g)) The ammonium salt value was determined by titration with 0.1 N aqueous silver nitrate solution using a 5% aqueous potassium chromate solution as an indicator, and then converted to the equivalent of potassium hydroxide, indicating the ammonium salt value of the non - volatile content.

[0186] <Method for manufacturing the micronized pigment> (Micronized pigment (A - 1)) 100 parts of C.I. Pigment Red 269 (PR269) ("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 Co., Ltd.) and kneaded at 70 °C for 5 hours. This mixture was poured into 4000 parts of warm water, stirred with a high - speed mixer for about 1 hour while heating to about 80 °C to form a slurry, and then filtered and washed with water repeatedly to remove salt and solvent, and then dried at 80 °C for 24 hours to obtain the micronized pigment (A - 1).

[0187] (Micronized pigment (A - 2)) Anthraquinone-based red pigment C.I. Pigment Red 177 ("Sinilex Red SR3C" manufactured by Ciba-Geigy): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts 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 put into 5 liters of warm water, stirred for 1 hour while heating to 70°C to form a slurry, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. After that, it was dried at 80°C for one day and night to obtain a micronized pigment (A-2).

[0188] (Micronized pigment (A-3)) 200 parts of diketopyrrolopyrrole-based red pigment C.I. Pigment Red 254 ("B-CF" manufactured by BASF Japan), 1400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho), and kneaded at 80°C for 6 hours. Next, this kneaded product was put into 8000 parts of warm water, stirred for 2 hours while heating to 80°C to form a slurry, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. After that, it was dried at 85°C for one day and night to obtain 190 parts of a micronized pigment (A-3).

[0189] (Micronized pigment (A-4)) 500 parts of phthalocyanine-based green pigment 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 put into 5 liters of warm water, stirred for 1 hour while heating to 70°C to form a slurry, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. After that, it was dried at 80°C for one day and night to obtain 490 parts of a micronized pigment (A-4).

[0190] (Micronized pigment (A-5)) 100 parts of phthalocyanine-based green pigment C.I. Pigment Green 58 (DIC's "FASTGEN GREEN A110"), 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, stirred for 1 hour while heating to 70°C to form a slurry, and filtered and washed repeatedly to remove sodium chloride and diethylene glycol. Then, it was dried at 80°C for a whole day and night to obtain 97 parts of micronized pigment (A-5).

[0191] (Micronized pigment (A-6)) 100 parts of C.I. Pigment Yellow 139 (BASF Japan's "Irgaphor Yellow 2R-CF"), 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, stirred for 1 hour while heating to 70°C to form a slurry, and filtered and washed repeatedly to remove sodium chloride and diethylene glycol. Then, it was dried at 80°C for a whole day and night to obtain micronized pigment (A-6).

[0192] (Micronized pigment (A-7)) 100 parts of a metal complex-based yellow pigment (C.I. Pigment Yellow 150, manufactured by Lanxess "Yellow Pigment E4GN"), 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, stirred with a high-speed mixer for about 1 hour while heating to about 80°C to form a slurry, and filtered and washed repeatedly to remove sodium chloride and the solvent. Then, it was dried at 80°C for a whole day and night to obtain micronized yellow pigment (A-7).

[0193] (Micronized pigment (A-8)) According to the synthesis method described in JP-A-2017-171915, an azobarbituric acid precursor was prepared. (Instruction 1) 46.2 parts of diazobarbituric acid and 38.4 parts of barbituric acid were introduced into 1100 parts of distilled water at 85°C. Subsequently, the pH was adjusted to about pH 5 using an aqueous potassium hydroxide solution, and stirring was continued for 90 minutes. Subsequently, the azobarbituric acid (0.3 mol) prepared in Instruction 1 was mixed with 1500 parts of distilled water at 82°C. Then, 10 parts of 30% hydrochloric acid was added dropwise to adjust the pH to 2 - 2.5. Thereafter, 79.4 parts of melamine (0.63 mol) was added. Next, a mixed solution of 0.225 mol of 25% nickel chloride + 0.075 mol of 25% zinc chloride was added dropwise. After 3 hours at 82°C elapsed, the pH was adjusted to about 5.5 using an aqueous potassium hydroxide solution. Subsequently, it was diluted with about 100 parts of distilled water at 90°C. Then, 21 parts of 30% hydrochloric acid was added dropwise, and the temperature of 90°C was maintained for 12 hours. Then, the pH was adjusted to about 5 using an aqueous potassium hydroxide solution. Then, the pigment was isolated on a suction filter, washed, dried at 80°C in a vacuum drying cabinet, and ground in a standard laboratory mill for 2 minutes to obtain a melamine adduct of zinc / nickel azobarbituric acid, a hybrid compound having a composition of 25 mol% Zn and 75 mol% nickel. 100 parts of the above hybrid compound, 10 parts of a dye derivative (d-1), 1000 parts of sodium chloride, and 120 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 8 hours. This mixture was poured into 2000 parts of warm water, stirred with a high-speed mixer for about 1 hour while heating to about 80°C to form a slurry, and after repeating filtration and washing with water to remove sodium chloride and the solvent, it was dried at 80°C for 24 hours and finely processed to obtain a finely divided metal azo pigment (A-8).

[0194] (Finely divided pigment (A-9)) 50 parts of C.I. Pigment Yellow 185 (“Paliotol Yellow L 1155” manufactured by BASF Japan), 250 parts of sodium chloride, and 25 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 100 °C for 6 hours. Next, this kneaded product was put into 5 liters of warm water and stirred for 1 hour while heating to 70 °C to form a slurry, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. Then, it was dried at 80 °C for a whole day and night to obtain a micronized pigment (A-9). The volume-average primary particle diameter of the obtained colorant was 33 nm.

[0195] (Micronized pigment (A-10)) 100 parts of the blue pigment C.I. Pigment Blue 15:6 (“Leonol Blue ES” manufactured by Toyo Color), 800 parts of crushed salt, and 100 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70 °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, and filtration and washing with water were repeated to remove salt and the solvent. Then, it was dried at 80 °C for 24 hours to obtain 98 parts of a micronized pigment (A-10).

[0196] (Micronized pigment (A-11)) Phthalocyanine-based blue pigment C.I. Pigment Blue 15:3 (PB15:3, manufactured by Toyo Color “LIONOL BLUE FG-7351” 200 parts, sodium chloride 600 parts, and 600 parts of diethylene glycol were charged into a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 80 °C for 6 hours. Next, this kneaded product was put into 8000 parts of warm water and stirred for 8 hours while heating to 120 °C to form a slurry, and filtration and washing with water were repeated to remove sodium chloride and diethylene glycol. Then, it was dried at 85 °C for a whole day and night, and a micronized pigment (A-11) was obtained.

[0197] (Micronized pigment (A-12)) 100 parts of purple pigment C.I. Pigment Violet 23 (LIONOGEN VIOLET FG-6140 manufactured by Toyo Color Co., Ltd.), 800 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 70 °C for 12 hours. This mixture was poured into 3000 parts of warm water and stirred with a high-speed mixer for about 1 hour while heating to about 70 °C to form a slurry. After repeating filtration and washing with water to remove salt and solvent, it was dried at 80 °C for 24 hours to obtain 95 parts of micronized pigment (A-12).

[0198] Table 1 shows the average primary particle diameter (nm) of each micronized pigment.

Table 1

[0199] <Method for manufacturing dye> (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, after uniformly mixing 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, it was charged into a dropping funnel, attached to the four-neck separable flask, and dropped over 2 hours. Two hours after the completion of dropping, 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.

[0200] (Dye 01 (AR52-JK)) The dye 01 (AR52-JK), which is a salt-forming compound composed of C.I. Acid Red 52 and Resin 1 having a cationic group in the side chain, was produced according to the following procedure. 30 parts of Resin 1 having a cationic group in the side chain in terms of non-volatile content was added to 2000 parts of water, and after thorough stirring and mixing, it 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 was gradually added dropwise to the above resin solution. After the addition, it 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 a salt-forming compound was obtained. After allowing it to cool to room temperature while stirring, suction filtration was carried out, and after washing with water, the salt-forming compound remaining on the filter paper was dried in a dryer to remove moisture and dried to obtain 32 parts of the dye 01 (AR52-JK), 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 dye 01 (AR52-JK) was 25% by mass.

[0201] <Method for producing dye solution> (Dye solution (DS-01)) The following mixture was stirred and mixed uniformly and then filtered through a filter with a pore size of 5.0 μm to prepare a dye solution (DS-01). Dye 01: 16.0 parts Propylene glycol monomethyl ether acetate: 84.0 parts

[0202] <Basic pigment derivative> The following basic pigment derivatives were used.

[0203] Basic pigment derivative (1)

Chemical formula

[0204] Basic pigment derivative (2)

Chemical formula

[0205] Basic pigment derivative (3) [Chemical formula]

[0206] (Production of resin (B1-1)) Into a flask equipped with a stirring device, a dropping funnel, a condenser, a thermometer, and a gas inlet tube, 149.3 parts of propylene glycol monomethyl ether was placed, and then it was stirred while purging with nitrogen and heated to 78 °C. Next, 16.1 parts of 2-(3,5-dimethylpyrazol-1-yl)carbonylaminoethyl methacrylate (Karenz MOI-BP, manufactured by Showa Denko KK), 6.7 parts of styrene, 28.2 parts of dicyclopentanyl methacrylate, 11.0 parts of methacrylic acid, 25.3 parts of 2-ethylhexyl methacrylate, and 12.8 parts of methyl methacrylate were added to the monomer mixture, and a solution prepared by adding and dissolving 11.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) (polymerization initiator) in 62.8 parts of propylene glycol monomethyl ether acetate was each dropped into the flask from the dropping funnel. After completion of the dropping, the mixture was stirred at 78 °C for 3 hours to carry out a copolymerization reaction to produce a copolymer. Thereafter, propylene glycol monomethyl ether acetate was added so that the nonvolatile content became 20% to obtain a resin (B1-1) having a block isocyanate group-containing structural unit. The weight average molecular weight of the copolymer in the obtained polymer composition was 8,100, and the acid value was 80 KOHmg / g.

[0207] (Production of resins (B1-2 to 4)) A copolymerization reaction was carried out under the same conditions as the alkali-soluble binder resin solution (B1-1) having a blocked isocyanate group-containing structural unit, except that the raw materials described in Table 2 were used, to obtain alkali-soluble binder resin solutions (B2-2 to 4) having a structural unit having a blocked isocyanato group. The weight average molecular weight and acid value of the copolymer in the obtained polymer composition are shown in Table 1-2. In Table 1, 2-[O-(1'-methylpropylideneamino)carboxamido]ethyl methacrylate is manufactured by Showa Denko K.K., Karenz MOI-BM), and malonic acid-2-[[[2-methyl-1-oxo-2-propenyl]oxy]ethyl]amino]carbonyl]-1,3-diethyl ester is manufactured by Showa Denko K.K., Karenz MOI-DEM).

[0208]

Table 2

[0209] (Production of resin (B1-5)) 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 K.K.), 50 parts of propylene glycol monomethyl ether acetate, 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 were 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 was half-esterified, and the reaction was terminated. The non-volatile content was adjusted to 20% with propylene glycol monomethyl ether acetate to obtain a resin (B1-5) having an acid value of 42 mgKOH / g and a weight average molecular weight of 9000.

[0210] (Production of resin (B2-1)) 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 (methoxypropyl acetate), 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 acid value measurement 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 non-volatile content measurement 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 (B2-1) solution with a non-volatile content of 20%. The acid value of the obtained resin was 68, the unsaturated double bond equivalent was 1593, and the weight average molecular weight was 13000.

[0211] (Production of Resin (B2-2)) Into a separable four-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping funnel, and a stirrer, 207 parts of cyclohexanone was charged, and the temperature was raised to 80 °C. After purging the inside of the reaction vessel with nitrogen, a mixture of 20 parts of methacrylic acid, 20 parts of para-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 another 3 hours to obtain a copolymer resin solution. Next, with respect to the total amount of the obtained copolymer solution, nitrogen gas was stopped and dry air was injected for 1 hour while stirring, and then cooled to room temperature. Then, a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karenz MOI manufactured by Showa Denko KK), 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 another 1 hour to obtain a solution of an acrylic resin. 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. Cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content became 20% to prepare resin (B2-2). The weight average molecular weight (Mw) was 18,000.

[0212] (Production of Resin (B2-3)) 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, and the temperature was raised to 80 °C. After purging the inside of the flask with nitrogen, a mixture of 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 was added dropwise from the dropping tube over 2 hours. After the addition, the reaction was further carried out at 100 °C for 3 hours. Then, 1.0 part of azobisisobutyronitrile dissolved in 50 parts of cyclohexanone was added, and the reaction was continued at 100 °C for 1 hour. Next, the inside of 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 (100% 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 then the reaction was terminated to obtain a solution of an acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% 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 and heated and dried at 180 °C for 20 minutes to measure the non-volatile content. PGMAc was added to the previously synthesized resin solution so that the non-volatile content became 20% by mass to prepare a resin (B2-3) solution. The weight average molecular weight (Mw) was 19,000.

[0213] <Production Example of Other Resin (B3)> 196 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 as a reaction vessel, heated to 80 °C, and after replacing the inside of the reaction vessel with nitrogen, from the dropping funnel, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of p-cumylphenol ethylene oxide-modified acrylate (“Aronix M110” manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2’-azobisisobutyronitrile were added dropwise 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 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% to prepare a solution of another resin (B3) having a binder function. The weight average molecular weight (Mw) was 26,000.

[0214] (Production of basic resin type dispersant (Bb-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 (Bb-1) having 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 dried by heating at 180 °C for 20 minutes to measure the non-volatile content, and PGMAc was added to the previously synthesized basic resin type dispersant (Bb-1) so that the non-volatile content became 20% by mass to prepare a solution of the basic resin type dispersant (Bb-1) having an amino group, which is an A-B-A block polymer.

[0215] (Production of basic resin type dispersant (Bb-2)) A reaction vessel equipped with a gas inlet tube, a condenser, a stirring blade, and a thermometer was charged with 133 parts of PGMAc, and the temperature was raised to 110 °C while purging with nitrogen. A dropping funnel was charged with 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), 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 (Bb-2) having an amine value of 201 mgKOH / g per non-volatile content and a number average molecular weight of 3,800 (Mn) was obtained. A solution of the basic resin type dispersant (Bb-2) was diluted in the same manner as the solution of the basic resin type dispersant (Bb-2) so that the non-volatile content was 20% by mass to prepare a solution of the basic resin type dispersant (Bb-2) having an amino group, which is a random polymer.

[0216] <Method for producing a colored composition> [Production Example 1] (Preparation of colored composition (R-1)) The following mixture was stirred and mixed until homogeneous, then dispersed for 3 hours using a zirconia bead with a diameter of 0.5 mm in an Eye G mill (Eye G Japan's "Mini Model M-250 MKII"), and then filtered through a filter with a pore size of 5.0 μm to prepare a colored composition (R-1). Pigment (A-1): 20.5 parts Resin (B1-1: 20% non-volatile content solution): 2.0 parts Resin (B2-1: 20% non-volatile content solution): 16.0 parts Solvent (P): 61.5 parts

[0217] [Production Examples 2 to 35] (Preparation of colored compositions (R-2 to R-35)) Colored compositions (R-2 to R-35) were prepared in the same manner as in Production Example 1, except that the types and masses of the materials were changed as shown in Table 3. The dispersed particle diameters of the respective pigments are shown in Table 3.

[0218]

Table 3

[0219] <Method for producing photosensitive coloring composition> [Example 1] (Photosensitive coloring composition (X-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 (Y-1). Coloring composition (R-1: non-volatile content 20%): 70.0 parts Resin (B1-1: non-volatile content 20%): 10.0 parts Thermosetting compound (E-1): 0.2 part Thermosetting compound (E-2): 0.3 part Polymerizable monomer (F): 3.0 parts Photoinitiator (G): 1.8 parts Sensitizer (H): 0.2 part Thiol-based chain transfer agent (I): 0.4 part Polymerization inhibitor (J): 0.1 part UV absorber (K): 0.1 part Antioxidant (L): 0.1 part Leveling agent (M: non-volatile content 3%): 1.0 part Storage stabilizer (N): 0.1 part Silane coupling agent (O): 0.2 part Solvent (P): 12.5 parts

[0220] [Examples 2 to 53, Comparative Examples 1 to 3] (Preparation of photosensitive coloring compositions (X-2 to 56)) Photosensitive coloring compositions (X-2 to 56) were each prepared in the same manner as in Example 1, except that the types of the coloring composition and the resin solution having a binder function in Example 1 were changed as described in Table 4. In addition, each raw material is as follows.

[0221]

Table 4

[0222] <Thermosetting compound (E)> · Epoxy compound (E-1) (E-1-1) 1,2-Epoxy-4-(2-oxiranyl) cyclohexane adduct of 2,2'-bis(hydroxymethyl)-1-butanol [EHPE-3150 (manufactured by Daicel Corporation)] (E-1-2) Glycidyl etherified epoxy compound of sorbitol [Denacol EX611 (manufactured by Nagase ChemteX Corporation)] (E-1-3) Triglycidyl isocyanurate (E-1-1) to (E-1-3) were each mixed in the same amount to obtain epoxy compound (E-1). · Oxetane compound (E-2): 3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane [Aron Oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

[0223] <Polymerizable compound (F)> (F-1) Trimethylolpropane triacrylate [Aronix M309 (manufactured by Toagosei Co., Ltd.)] (F-2) Dipentaerythritol penta and hexaacrylate [Aronix M402 (manufactured by Toagosei Co., Ltd.)] (F-3) Polybasic acidic acrylic oligomer [Aronix M520 (manufactured by Toagosei Co., Ltd.)] (F-4) Caprolactone-modified dipentaerythritol hexaacrylate [KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]

[0224] (F-5) Polyfunctional urethane acrylate according to the following A 1.5-liter five-neck reaction vessel was charged with pentaerythritol triacrylate (432 g) and hexamethylene diisocyanate (84 g), and reacted at 60 °C for 8 hours to obtain a product containing a (meth)acryloyl group-containing polyfunctional urethane acrylate (F-5). In the product, the proportion of the polyfunctional urethane acrylate (F-5) was 70% by mass, and the balance was occupied by other photopolymerizable monomers. It was confirmed by IR analysis that no isocyanate groups were present in the reaction product.

[0225] (F-6) Bifunctional bisphenol A type (meth)acrylate [ABE-300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)] (F-7) Ethoxylated isocyanuric acid triacrylate [A-9300 (manufactured by Shin-Nakamura Chemical Co., Ltd.)] (F-8) Trimethylolpropane EO-modified triacrylate [Aronix M350 (manufactured by Toagosei Co., Ltd.)] (F-9) EO-modified (12) dipentaerythritol hexaacrylate [KAYARAD DPEA-12 (manufactured by Nippon Kayaku Co., Ltd.)] The above (F-1) to (F-9) were each mixed in the same amount to obtain a photopolymerizable monomer (E).

[0226] <Photopolymerization initiator (G)> (G-1) 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one [Irgacure 907 (manufactured by BASF Japan Ltd.)] (G-2) 2-(Dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone [Irgacure 379 (manufactured by BASF Japan Ltd.)] (G-3) 2,4,6-Trimethylbenzoyl-diphenyl-phosphine oxide [Lucirin TPO (manufactured by IGM Resins)] (G-4) 2,2'-Bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole [Biimidazole (manufactured by Kurokane Kasei Co., Ltd.)] (G-5) p-Dimethylaminoacetophenone [DMA (manufactured by Daiki Fine Co., Ltd.)] (G-6) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl], 1-(O-acetoxyoxime) [Irgacure OXE02 (manufactured by BASF Japan Ltd.)] (G-7) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one [Irgacure 2959 (manufactured by BASF Japan Ltd.)] (G-8) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide [Irgacure 819 (manufactured by BASF Japan Ltd.)]

[0227] (G-9) Photoinitiator obtained by the following synthesis method 100.0 parts of N-benzoylcarbazole were dissolved in 1000 parts of chloroform, and 85.0 parts of aluminum chloride were further added. While stirring at 0 °C, a solution prepared by dissolving 32.0 parts of propionyl chloride in 500 parts of chloroform was added dropwise over 2 hours. After the addition was completed, the mixture was stirred at 25 °C for 4 hours. The reaction solution was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, and after filtering off the desiccant, the residue was recrystallized from chloroform / methanol to obtain 113.0 parts of intermediate compound (a1). Next, when 100.0 parts of compound (a1) was dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid, 38.4 parts of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature. After the addition was completed, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 parts of ice water and extracted with 1600 parts of chloroform. The organic layer was washed with water (500 parts × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to obtain 99.8 parts of precursor compound (b1). Next, when 30.0 parts of compound (b1) was stirred in 300 parts of ethyl acetate, 6.3 parts of acetic anhydride and 10.6 parts of sodium acetate were added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution was poured into 500 parts of ice water, the resulting product was extracted with ethyl acetate, the organic layer was washed with water (300 parts × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was recrystallized from ethyl acetate - hexane to obtain 31.4 g of the oxime ester-based photopolymerization initiator (G-9).

[0228] Photopolymerization initiator (G-9)

Chemical formula

[0229] (G-10) The photopolymerization initiator obtained by the following synthesis method 100.0 parts of N-benzoylcarbazole were dissolved in 1000 parts of chloroform. Further, 84.0 parts of aluminum chloride were added, and while stirring at 0 °C, a solution prepared by dissolving 36.8 parts of butanoyl chloride in 500 parts of chloroform was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred at 25 °C for 4 hours. The reaction solution was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, and after filtering off the desiccant, the residue was recrystallized from chloroform / methanol to obtain 109.3 parts of intermediate compound (a2). Next, when 100.0 parts of compound (a2) were dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid, 43.1 parts of tert-butyl nitrite were added dropwise over 1 hour while stirring at room temperature. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 parts of ice water and extracted with 1600 parts of chloroform. The organic layer was washed with water (500 parts × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to obtain 89.3 parts of precursor compound (b2). Next, when 30.0 parts of compound (b2) were stirred in 300 parts of ethyl acetate, 6.1 parts of acetic anhydride and 10.3 parts of sodium acetate were added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution was poured into 500 parts of ice water, the resulting product was extracted with ethyl acetate, the organic layer was washed with water (300 parts × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was recrystallized from ethyl acetate-hexane to obtain 30.0 parts of oxime ester-based photoinitiator (G-10).

[0230] Photoinitiator (G-10) [Chemical formula]

[0231] (G-11) A photoinitiator obtained by the following synthesis method 100.0 parts of N-(p-nitrophenyl)carbazole were dissolved in 1000 parts of chloroform. Further, 101.8 parts of aluminum chloride were added, and while stirring at 0 °C, a solution prepared by dissolving 44.3 parts of butanoyl chloride in 500 parts of chloroform was added dropwise over 2 hours. After completion of the dropwise addition, the mixture was stirred at 25 °C for 4 hours. The reaction solution was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, and after filtering off the desiccant, the residue was recrystallized from chloroform / methanol to obtain 113.6 parts of intermediate compound (a3). Next, when 100.0 parts of compound (a3) were dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid, 43.1 parts of tert-butyl nitrite were added dropwise over 1 hour while stirring at room temperature. After completion of the dropwise addition, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 parts of ice water and extracted with 1500 parts of chloroform. The organic layer was washed with water (500 parts × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to obtain 107.2 parts of precursor compound (b3). Next, when 50.0 parts of compound (b3) were stirred in 500 parts of ethyl acetate, 19.9 parts of acetic anhydride and 11.7 parts of sodium acetate were added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution was poured into 500 parts of ice water, the resulting product was extracted with ethyl acetate, the organic layer was washed with water (500 parts × 3 times), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was recrystallized from ethyl acetate - hexane to obtain 57.6 parts of oxime ester-based photopolymerization initiator (G-11).

[0232] Photopolymerization initiator (G-11) [Chemical formula]

[0233] (G-12) A photopolymerization initiator obtained by the following synthesis method 100.0 parts of N-benzoyl-1,3-dimethylcarbazole were dissolved in 1000 parts of chloroform, and 78.6 parts of aluminum chloride was further added. While stirring at 0 °C, a solution prepared by dissolving 29.6 parts of propionyl chloride in 500 parts of chloroform was added dropwise over 2 hours. After the addition was completed, the mixture was stirred at 25 °C for 4 hours. The reaction solution was poured into 2000 parts of ice water and extracted with 2000 parts of chloroform. The organic layer was dried over magnesium sulfate, the desiccant was filtered off, and the residue was recrystallized from chloroform / methanol to obtain 111.8 parts of the intermediate compound (a4). Next, when 100.0 parts of the compound (a4) was dissolved in a mixed solution of 1000 parts of tetrahydrofuran and 500 parts of concentrated hydrochloric acid, 35.7 parts of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature. After the addition was completed, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 parts of ice water and extracted with 1600 parts of chloroform. The organic layer was washed with water (3 times with 500 parts each), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was washed with n-hexane to obtain 98.3 parts of the precursor compound (b4). Next, when 30.0 parts of the compound (b4) was stirred in 300 parts of ethyl acetate, 5.9 parts of acetic anhydride and 10.0 parts of sodium acetate were added, and the mixture was heated to reflux for 3 hours. Thereafter, the reaction solution was poured into 500 parts of ice water, the resulting product was extracted with ethyl acetate, the organic layer was washed with water (3 times with 300 parts each), dried over magnesium sulfate, the desiccant was filtered off, the solvent was distilled off, and the residue was recrystallized from ethyl acetate - hexane to obtain 31.2 parts of the oxime ester-based photopolymerization initiator (G-12).

[0234] Photopolymerization initiator (G-12) [Chemical formula] As described above, (G-1) to (G-12) were mixed in equal amounts to obtain the photopolymerization initiator (G).

[0235] <Sensitizer (H) > (H-1) 2,4 - Diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)] (H-2) 4,4'-Bis(diethylamino)benzophenone [CHEMARK DEABP (manufactured by Chemark Chemical)] The above (H-1) and (H-2) were mixed in equal amounts to prepare sensitizer (H).

[0236] <Thiol-based chain transfer agents (I)> (I-1) 2-Ethylhexyl-3-mercaptopropionate [BMPA-2EH (manufactured by Yodo Chemical)] (I-2) Trimethylolethane tris(3-mercaptobutyrate) [TEMB (Showa Denko)] (I-3) Trimethylolpropane tris(3-mercaptobutyrate) [TPMB (Showa Denko)] (I-4) Pentaerythritol tetrakis(3-mercaptopropionate) [PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (I-5) Trimethylolpropane tris(3-mercaptopropionate) [TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)] (I-6) Tris[(3-mercaptopropionyloxy)-ethyl]isocyanurate [TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)] As described above, (I-1) was used alone or (I-2) to (I-6) were mixed in equal amounts and used as a thiol-based chain transfer agent (IM).

[0237] <Polymerization inhibitor (J)> (J-1) 3-Methylcatechol (J-2) Methylhydroquinone (J-3) tert-Butylhydroquinone The above (J-1) to (J-3) were mixed in equal amounts to prepare a polymerization inhibitor (J).

[0238] <Ultraviolet absorber (K)> (K-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.)] (K-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN 900 (manufactured by BASF Japan Ltd.)] The above (K-1) and (K-2) were each mixed in the same amount to obtain an ultraviolet absorber (K).

[0239] <Antioxidant (L)> (L-1) Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (L-2) Dioctadecyl 3,3'-thiodipropionate (L-3) Tris[2,4-di-(tert)-butylphenyl]phosphine (L-4) Bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate (L-5) p-Octylphenyl salicylate The above (L-1) to (L-5) were each mixed in the same amount to obtain an antioxidant (L).

[0240] <Leveling agent (M)> 1 part of "BYK-330" manufactured by BYK Chemie GmbH, 1 part of "Megafac F-551" manufactured by DIC Corporation, 1 part of "Emulgen 103" manufactured by Kao Corporation A mixed solution obtained by dissolving the above in 97 parts of PGMAc.

[0241] <Storage stabilizer (N)> (N-1) 2,6-Bis(1,1-dimethylethyl)-4-methylphenol (manufactured by Honshu Chemical Industry Co., Ltd. "BHT")[[]]END]] (N-2) Triphenylphosphine (manufactured by Kitakyo Chemical Industry Co., Ltd. "TPP")[[]]END]] As described above, (N - 1) and (N - 2) were each mixed in the same amount to obtain a storage stabilizer (N).

[0242] <Adhesion improver (O)> (O - 1) 3 - Glycidoxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM - 403 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (O - 2) 3 - Methacryloxypropyltriethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBE - 503 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (O - 3) N - 2-(Aminoethyl)-3 - aminopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM - 603 (manufactured by Shin-Etsu Chemical Co., Ltd.)] (O - 4) 3 - Mercaptopropyltrimethoxysilane [Shin-Etsu Silicone Silane Coupling Agent KBM - 803 (manufactured by Shin-Etsu Chemical Co., Ltd.)] As described above, (O - 1) to (O - 4) were each mixed in the same amount to obtain a silane coupling agent (O).

[0243] <Solvent (P)> (P - 1) PGMAc 30 parts (P - 2) Cyclohexanone 30 parts (P - 3) Ethyl 3 - ethoxypropionate 10 parts (P - 4) Propylene glycol monomethyl ether 10 parts (P - 5) Cyclohexanol acetate 10 parts (P - 6) Dipropylene glycol methyl ether acetate 10 parts As described above, (P - 1) to (P - 6) were each mixed in the above parts by mass to obtain a solvent (P).

[0244] <Evaluation of photosensitive coloring composition> For the photosensitive coloring compositions (X - 1 to X - 56), each test was conducted by the following method. The test results are shown in a table. In addition, each evaluation criterion is as follows. ◎: Particularly good level. 〇: Good level. △: Practical level. ×: Non - practical level.

[0245] <Evaluation of Fine Pattern Formation> The formation of fine patterns was evaluated in terms of linearity and pattern shape as follows. [Preparation of Evaluation Substrate] The obtained photosensitive coloring composition was applied to a glass substrate of 10 cm in length and 10 cm in width by spin - coating method. After that, it was heated in a clean oven at 70 °C for 15 minutes to remove the solvent, and a coating film of about 1 μm was obtained. Then, after cooling this substrate to room temperature, ultraviolet rays of 600 mJ / cm 2 were exposed through a photomask of stripe patterns with a width of 100 μm (pitch 200 μm) and 25 μm (pitch 50 μm) using an ultra - high - pressure mercury lamp. After that, this substrate was spray - developed using an aqueous sodium carbonate solution at 23 °C, then washed with ion - exchanged water, air - dried, and heated in a clean oven at 100 °C for 30 minutes. The spray development was carried out at the shortest time capable of forming a pattern without remaining development for each coating film of the photosensitive coloring composition, and this was defined as the appropriate development time. The film thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

[0246] [Linearity Evaluation] Regarding the pattern in the 100 - μm - width photomask part of the filter segment formed by the above method, observation and evaluation were carried out using an optical microscope. The evaluation ranks are as follows. ○: Good linearity △: Partially poor linearity ×: Poor linearity

[0247] [Pattern Shape Evaluation] Regarding the cross - section of the pattern in the 100 - μm photomask part of the filter segment formed by the above method, observation and evaluation were carried out using an electron microscope. The cross - section of the pattern has a good smooth taper. The evaluation ranks are as follows. ◎: Cross - section is a smooth tapered shape ○: Cross - section is a tapered shape ×: The cross-section has an inverse taper shape

[0248] (Chemical resistance) The obtained photosensitive coloring composition was spin-coated onto a glass substrate using a spin coater so that the dry film thickness was 0.9 μm, and dried at 70 °C for 20 minutes. Next, for the dried coating film, exposure was performed with an ultra-high pressure mercury lamp with an i-line illuminance of 30 mW / cm 2 at 600 mJ / cm 2 . The pattern-exposed coating film was developed with an unexposed portion using a 2 mass% potassium hydroxide aqueous solution, and then washed with pure water. Thereafter, water droplets were blown off with high-pressure air, and the substrate was naturally dried, and post-baked on a hot plate at 120 °C for 10 minutes to form a pattern on the glass substrate. The spectral transmittance of the patterned portion of the glass substrate was measured using a microspectrophotometer ("OSP-SP100" manufactured by Olympus Optical Co., Ltd.). Thereafter, it was immersed in an aqueous solution in which TMAH (tetramethylammonium hydroxide) was dissolved at a concentration of 1.0 wt% in water, and the spectral transmittance was promoted again. The change in transmittance at 400 nm before and after immersion in the TMAH aqueous solution was evaluated. The evaluation ranks are as follows. ◎: The change in transmittance is less than 0.5% 〇: The change in transmittance is 0.5% or more and less than 1.0% △: The change in transmittance is 1.0% or more and less than 5.0% ×: The change in transmittance is 5.0% or more

[0249] (Viscosity characteristics) For the obtained photosensitive coloring composition, the viscosity at a rotational speed of 20 rpm was measured using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.). The evaluation ranks are as follows. 〇: Viscosity 2.0 or more and less than 10.0: Good level ×: Viscosity 10.0 or more: Unusable level

[0250] (Storage stability) The storage stability was evaluated by the following method. The initial viscosity on the day after preparing the photosensitive coloring composition and the viscosity over time promoted over 1 week at 40°C were measured at 25°C under the condition of a rotation speed of 50 rpm using an E-type viscometer ("ELD-type viscometer" manufactured by Toki Sangyo Co., Ltd.). From the values of this initial viscosity and viscosity over time, the rate of change in viscosity over time was calculated using the following formula, and the storage stability was evaluated in two stages. [Rate of change in viscosity over time]=|([Initial viscosity] - [Viscosity over time]) / [Initial viscosity]| × 100 ○: The rate of change is less than 10% ×: The rate of change is 10% or more

[0251]

Table 5

Claims

1. A photosensitive coloring composition used for forming a pattern of a color filter by a photolithography method in which the pattern is cured in a heating step at 150 °C or lower after development, comprising a pigment (A), a resin (B), a photopolymerization initiator (C), and a polymerizable compound (D), wherein the resin (B) contains a resin (B1) containing a blocked isocyanate group-containing structural unit and a resin (B2) containing a (meth)acryloyl group-containing vinyl polymer moiety, the resin (B2) is further a resin having an aromatic carboxylic acid moiety, the content of the pigment (A) is 45% by mass to 70% by mass in the total nonvolatile components, and the acid values of both the resin (B1) and the resin (B2) are 50 to 160 (mgKOH / g), and the photosensitive coloring composition is characterized by this.

2. The photosensitive coloring composition according to Claim 1, wherein the resin (B1) further has a carboxy group-containing structural unit.

3. The photosensitive coloring composition according to Claim 1 or 2, wherein the total amount of the resin (B1) and the resin (B2) is 80% by mass or more in the total amount of the resin (B).

4. The photosensitive coloring composition according to any one of Claims 1 to 3, further comprising one or more of a basic pigment derivative and a basic resin type dispersant.

5. A cured film which is a cured product of the photosensitive coloring composition according to any one of Claims 1 to 4.

6. A color filter having the cured film according to Claim 5.

7. A solid-state imaging device comprising the color filter according to Claim 6.

8. An image display device comprising the color filter according to Claim 6.

Images