Photosensitive coloring composition and its use

Abstract

To provide a photosensitive coloring composition which enables formation of a good pattern shape after development and can suppress occurrence of wrinkles after post baking, and enables formation of a film having high light-shielding property and low external light reflection property.SOLUTION: A photosensitive coloring composition contains a black coloring agent (A), a dispersion resin (B), a polymerizable compound (C) and a photopolymerization initiator (D), wherein the photopolymerization initiator (D) contains a compound (D1) represented by the following general formula (1) and an oxime-based photopolymerization initiator (D2). In the general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms; and R3 represents a hydrogen atom or a monovalent substituent.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a photosensitive coloring composition containing a black colorant, and uses thereof. [Background technology]

[0002] 2. Description of the Related Art Color filters used in image display devices such as liquid crystal displays and organic electroluminescence displays include a light-shielding filter called a black matrix for the purpose of blocking light between pixels and improving contrast. In addition, solid-state imaging elements such as C-MOS (Complementary Metal Oxide Semiconductor) image sensors and CCD (Charge Coupled Device) image sensors used in imaging devices such as smartphones and tablet terminals are equipped with light-shielding filters to prevent noise generation and improve image quality.

[0003] Compositions used to form light-shielding filters include compositions containing black colorants such as carbon black and titanium black. For example, Patent Document 1 discloses a light-shielding film-forming composition containing carbon black or titanium black with an average particle diameter of 40 nm or less and a resin component, which can form a coating film arranged around the periphery of the effective pixel region of a solid-state imaging device. Patent Document 2 also discloses a photosensitive composition for forming partition walls in optical elements, which contains an alkali-soluble resin having a photocurable ethylenically unsaturated double bond, a photopolymerization initiator, a black pigment, and hollow fine particles with an average primary particle diameter of 20 to 100 nm. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Laid-Open No. 2006-156801 [Patent Document 2] Japanese Patent Application Laid-Open No. 2011-48195 Summary of the Invention [Problem to be solved by the invention]

[0005] However, while cured films formed from conventional compositions have excellent light-blocking properties, they have the problem of reflecting light entering an image display device (hereinafter also referred to as external light reflection). Furthermore, they have problems with the pattern shape, such as pattern chipping after alkaline development due to insufficient photocuring and pattern peeling from the substrate. Furthermore, they have problems such as wrinkles occurring on the pattern surface after heat treatment (hereinafter also referred to as post-baking).

[0006] The present invention aims to provide a photosensitive coloring composition that can form a good pattern shape after development, can suppress the occurrence of wrinkles after post-baking, and can form a coating film that has high light-blocking properties and low external light reflectivity. [Means for solving the problem]

[0007] The present invention provides a photosensitive coloring composition comprising a black colorant (A), a dispersing resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), The photosensitive coloring composition relates to the photopolymerization initiator (D), which contains a compound (D1) represented by the following general formula (1) and an oxime-based photopolymerization initiator (D2). General formula (1) [ka] (In general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R3 represents a hydrogen atom or a monovalent substituent.) [Effects of the Invention]

[0008] According to the present invention, there can be provided a photosensitive coloring composition capable of forming a coating film having a good pattern shape after development, suppressing the occurrence of wrinkles after post-baking, and having high light-blocking properties and low external light reflectivity. The present invention also can provide a cured film, a light-blocking filter, a color filter, an image display device, and a solid-state imaging device. DETAILED DESCRIPTION OF THE INVENTION

[0009] Hereinafter, the embodiment for carrying out the photosensitive coloring composition of the present invention will be described in detail. Note that the present invention is not limited to the following embodiment, and can be modified and carried out within a range that can solve the problem.

[0010] In the present invention, unless otherwise specified, "(meth)acryloyl," "(meth)acrylic," "(meth)acrylic acid," "(meth)acrylate," or "(meth)acrylamide" means "acryloyl and / or methacryloyl," "acrylic and / or methacrylic," "acrylic acid and / or methacrylic acid," "acrylate and / or methacrylate," or "acrylamide and / or methacrylamide," respectively. Furthermore, "CI" refers to the Color Index (CI; published by The Society of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond. Furthermore, the molecular weight of the compound in the present invention is a calculated value or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry) for low molecular weight compounds whose molecular weight can be specified, and is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography using tetrahydrofuran as a solvent for compounds having a molecular weight distribution. A monomer is a compound that polymerizes to form a resin. A monomer is in an unreacted state, and a monomer unit is a monomer that forms a resin after polymerization.

[0011] <Photosensitive coloring composition> The photosensitive coloring composition of the present invention is a photosensitive coloring composition containing a black colorant (A), a dispersing resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), The photosensitive coloring composition is characterized in that the photopolymerization initiator (D) contains a compound (D1) represented by the following general formula (1) and an oxime-based photopolymerization initiator (D2). General formula (1) [ka] (In general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R3 represents a hydrogen atom or a monovalent substituent.)

[0012] The mechanism by which the photosensitive coloring composition having the above-mentioned constitution can solve the problems of the present invention is not clear, but is speculated as follows.

[0013] Photosensitive coloring compositions containing colorants such as carbon black and forming black coatings have high light-blocking properties over a wide wavelength range. However, when a coating formed from the photosensitive coloring composition is pattern-exposed to ultraviolet light such as g-line, h-line, or i-line, the light does not reach the inside of the coating, resulting in poor pattern shape such as chipping or peeling of the cured film during alkaline development, and wrinkles on the surface due to a difference in thermal curing shrinkage between the inside and the surface during post-baking. This results in a decrease in optical density and a deterioration in light-blocking properties. However, we speculate that compound (D1) represented by general formula (1) has a rigid fluorene structure, which makes it less susceptible to shrinkage during curing and reduces wrinkles compared to photopolymerization initiators such as 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one and 2-(dimethylamino)-1-(4-morpholinophenyl)-2-benzyl-1-butanone, which have traditionally been widely used in the color filter field. Furthermore, by using a specific oxime-based photopolymerization initiator (D2), which has a different absorption wavelength from compound (D1) and is highly sensitive, the wavelength range of light available for photopolymerization is expanded, improving reactivity. Therefore, we speculate that light penetrates deep into the coating, promoting the reaction, reducing wrinkles and improving pattern shape.

[0014] [Black colorant (A)] The photosensitive coloring composition of the present invention contains a black colorant (A).

[0015] The black colorant (A) may be a single colorant, or a mixture of two or more colorants to produce a black or nearly black appearance. Examples of the black colorant (A) include pigments and dyes, with pigments being preferred from the viewpoints of light resistance, heat resistance, and solvent resistance.

[0016] Examples of the pigment include inorganic pigments and organic pigments.

[0017] (inorganic pigments) Examples of inorganic pigments include metal oxides, metal nitrides, and metal oxynitrides containing one or more metal elements selected from the group consisting of Group 4 metal elements such as titanium and zirconium, Group 5 metal elements such as vanadium and niobium, cobalt, chromium, copper, manganese, ruthenium, iron, nickel, tin, and silver, as well as carbon black. Two or more of these inorganic pigments may be used in combination, and organic pigments or dyes, as described below, may also be used in combination to enhance light-blocking properties. Among these, carbon black is preferred because it is inexpensive and can form a film with high light-blocking properties in small amounts.

[0018] Examples of carbon black include lamp black, acetylene black, thermal black, channel black, furnace black, etc. Among these, furnace black is preferred.

[0019] The average primary particle diameter of carbon black is preferably 10 to 30 nm, more preferably 10 to 20 nm. A moderate particle diameter facilitates achieving both light-blocking properties and curability. The average primary particle diameter is determined by averaging approximately 20 random particles displayed in a magnified image (approximately 1,000 to 10,000 times) of a cross section of a film formed from the photosensitive coloring composition using a scanning electron microscope. When particles have lengths in the major and minor axis directions, the length in the major axis direction is used.

[0020] The specific surface area of carbon black is 100 to 500 m from the viewpoint of light blocking properties. 2 / g is preferred, and 150 to 400m 2 / g is more preferable. The specific surface area can be measured by a known method. For example, the specific surface area can be determined by adsorbing iodine, nitrogen (BET method, STSA method), cetyltrimethylammonium bromide, or the like onto the surface of carbon black. Among these, the nitrogen BET method is preferred.

[0021] Examples of commercially available carbon black products include #30, 30L, 32, 40, 44, 45, 45L, 47, 52, 650, 850, 900, 950, 960, 980, 1000, 1000N, 2300, 2350, 2600, 2650, 3230, 3400, 4000, MCF88, MA7, 8, 11, 77, 100, 230, and 600 manufactured by Mitsubishi Chemical Corporation, and BLACK PEARLS 460, 800, 880, 900, 1000, 4840, 1300, 1400, L, and REGAL 330, 400, and 600 manufactured by CABOT Corporation.

[0022] (organic pigments) Examples of organic pigments include perylene compounds such as CI Pigment Black 21, 30, 31, 32, 33, and 34; bisbenzofuranone compounds described in JP-A-2010-534726, JP-A-2012-515233, and JP-A-2012-515234; and black organic pigments such as azomethine compounds described in JP-A-1-170601 and JP-A-2-34664.

[0023] Alternatively, two or more organic pigments selected from the group consisting of red organic pigments, yellow organic pigments, green organic pigments, blue organic pigments, and purple organic pigments may be used to form the black colorant (A). In this case, examples of the combination that produces black include the following: (1) Contains a yellow organic pigment and a purple organic pigment. (2) Contains a red organic pigment, a yellow organic pigment, and a purple organic pigment. (3) Contains a red organic pigment, a yellow organic pigment, and a blue organic pigment. (4) Contains a red organic pigment, a yellow organic pigment, and a green organic pigment. (5) Contains a yellow organic pigment, a blue organic pigment, and a purple organic pigment. (6) Contains a red organic pigment, a yellow organic pigment, a blue organic pigment, and a purple organic pigment.

[0024] An example of the above embodiment (1) is an embodiment in which the yellow organic pigment contains at least one selected from CI Pigment Yellow 139, 185, 231, and 233, and the purple organic pigment contains CI Pigment Violet 23. An example of the above embodiment (2) is an embodiment in which the red organic pigment contains at least one selected from CI Pigment Red 177, 254, 291, 295, and 296, the yellow organic pigment contains at least one selected from CI Pigment Yellow 139, 185, 231, and 233, and the purple organic pigment contains CI Pigment Violet 23. An example of the embodiment (3) above is an embodiment in which the red organic pigment contains at least one selected from CI Pigment Red 177, 254, 291, 295, and 296, the yellow organic pigment contains at least one selected from CI Pigment Yellow 139, 185, 231, and 233, and the blue organic pigment contains at least one selected from CI Pigment Blue 15:3, 15:4, and 15:6. An example of the embodiment (4) above is an embodiment in which the red organic pigment contains at least one selected from CI Pigment Red 177, 254, 291, 295, and 296, the yellow organic pigment contains at least one selected from CI Pigment Yellow 139, 185, 231, and 233, and the green organic pigment contains at least one selected from CI Pigment Green 7, 36, 58, 59, and 63. An example of the above embodiment (5) is an embodiment in which the yellow organic pigment contains at least one selected from CI Pigment Yellow 139, 185, 231, and 233, the blue organic pigment contains at least one selected from CI Pigment Blue 15:3, 15:4, and 15:6, and the purple organic pigment contains CI Pigment Violet 23. An example of the above embodiment (6) is an embodiment in which the red organic pigment contains at least one selected from CI Pigment Red 177, 254, 291, 295, and 296; the yellow organic pigment contains at least one selected from CI Pigment Yellow 139, 185, 231, and 233; the blue organic pigment contains at least one selected from CI Pigment Blue 15:3, 15:4, and 15:6; and the purple organic pigment contains CI Pigment Violet 23.

[0025] Among the above embodiments (1) to (6), the above embodiment (5) is preferred from the viewpoint of light-blocking properties.

[0026] Among the above-mentioned embodiments (5), CI Pigment Yellow 139 is more preferred as the yellow organic pigment, CI Pigment Blue 15:6 as the blue organic pigment, and CI Pigment Violet 23 as the purple organic pigment.

[0027] Table 1 shows the preferred mass ratios (mass %) of each organic pigment in each embodiment.

[0028] [Table 1]

[0029] (Other colorants) The photosensitive coloring composition of the present invention may contain other colorants in addition to the black colorant (A).

[0030] The other colorants are not particularly limited and may be appropriately selected from organic pigments, inorganic pigments, and dyes.

[0031] Examples of organic pigments include compounds classified as pigments in the Color Index. Specific examples include CI Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 57:1, 57:2, 58:4, 60, 61, 62, 63, 64, 65, 66, 67, 68, 69, 70, 71, 72, 73, 74, 75, 76, 77, 78, 79, 80, 81, 82, 83, 84, 85, 86, 87, 88, 89, 90, 91, 92, 93, 94, 95, 96, 97, 98, 99, 100, 101, 102, 103, 104, 105, 106, 107, 108, 109, 110, 111, 112, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 3,63:1,63:2,64,64:1,68,69,81,81:1,81:2,81:3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151,166,168,169,170,172,173,174,175,176,178, 179,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,255,256,257,258 ,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, pigments described in JP 2014-134712 A, and pigments described in JP 6368844 A; Orange organic pigments such as CI Pigment Orange 36, 38, 43, 62, 64, 71, 73; CI Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 121, 122, 123, 124, 125, 126, 127, 128, 129, 130, 131, 132, 133, 134, 135, 136, 137, 138, 139, 140, 141, 142, 143, 144, 145, 146, 147, 148, 149, 150, 151, 152, 153, 154, 155, 156, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 171 Yellow organic pigments such as those described in JP 2012-226110 A, JP 23, 126, 127, 128, 129, 138, 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, 187, 188, 192, 193, 194, 196, 198, 199, 213, 214, and JP 2012-226110 A; Green organic pigments such as CI Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, 63; Blue organic pigments such as CI Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 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; Examples of purple organic pigments include CI Pigment Violet 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0032] Examples of inorganic pigments include titanium oxide, silicon dioxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, iron blue, chromium oxide green, cobalt green, and amber.

[0033] Examples of dyes include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, sulfur dyes, etc. Derivatives of these dyes, lake forms of dyes, and salt-forming compounds may also be used.

[0034] From the viewpoint of light-shielding properties, the content of the black colorant (A) is preferably from 5 to 70 mass %, more preferably from 10 to 60 mass %, based on 100 mass % of the nonvolatile content of the photosensitive color composition.

[0035] (Fine pigment particle size) The pigment is preferably micronized before use. The micronization method is not particularly limited, and for example, wet milling, dry milling, or solution precipitation can be used. Among these, salt milling treatment using a kneader method, which is a type of wet milling, is preferred. The average primary particle diameter of the micronized pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. From the viewpoints of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

[0036] Salt milling is a process in which a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is mechanically kneaded under heat using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, or other kneading machine, and then the water-soluble inorganic salt and water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. Optimizing the conditions for salt milling a pigment can produce a pigment with an extremely fine primary particle size, a narrow distribution, and a sharp particle size distribution.

[0037] Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, and sodium sulfate, with sodium chloride (table salt) being preferred from the standpoint of cost. From the standpoint of both treatment efficiency and production efficiency, the amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, and more preferably 300 to 1,000 parts by mass, per 100 parts by mass of the pigment.

[0038] The water-soluble organic solvent functions to moisten the pigment and water-soluble inorganic salt. It is not particularly limited as long as it is soluble (miscible) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent becomes prone to evaporation, a high-boiling solvent with a boiling point of 120°C or higher is preferred for safety reasons. Examples of water-soluble organic solvents that can be used include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, and liquid polypropylene glycol. The amount of water-soluble organic solvent used is preferably 5 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

[0039] A resin may be added to the salt milling treatment as needed. The type of resin is not particularly limited, and examples include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. Among these, resins that are solid at room temperature and insoluble in water are preferred, and those that are partially soluble in the organic solvents are preferred. The amount of resin added is preferably 2 to 200 parts by mass per 100 parts by mass of the pigment.

[0040] [Dispersion resin (B)] The photosensitive coloring composition of the present invention contains a dispersing resin (B).

[0041] The dispersing resin (B) is preferably a resin having an adsorptive group that has a high affinity for the black colorant (A). The adsorptive group preferably has either a basic group or an acidic group, and from the viewpoints of developability and pattern shape, it is more preferable to include a dispersing resin (B1) having an acidic group.

[0042] Examples of the acidic group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, etc. Among these, from the viewpoint of developability, a carboxyl group and a phosphoric acid group are preferred, and a carboxyl group is more preferred.

[0043] (Dispersion resin (B1) having acidic groups) From the viewpoint of pattern shape, the dispersing resin (B) preferably contains a dispersing resin (B1) having an acidic group. Examples of the dispersing resin (B1) having an acidic group include the dispersing resins shown in the following (B1-1) or (B1-2).

[0044] [Dispersion resin (B1-1) having an acidic group] The dispersion resin (B1-1) having an acidic group is a resin containing a polyester portion having a carboxyl group, which is formed by reacting an acid anhydride group in one or more acid anhydrides selected from the group consisting of tetracarboxylic dianhydrides and tricarboxylic anhydrides with a hydroxyl group in a hydroxyl group-containing compound, and a vinyl polymer portion formed by radical polymerization of a monomer. First, the polyester moiety will be described. The polyester moiety is a site where a plurality of ester groups resulting from the reaction between an acid anhydride group and a hydroxyl group are present.

[0045] Examples of the tetracarboxylic dianhydride include 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentylacetic dianhydride, 3,5,6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofuryl)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, and bicyclo[2.2.Aliphatic tetracarboxylic dianhydrides such as 2-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfone tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride , 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenylethertetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilanetetracarboxylic dianhydride, 3,3',4,4'-tetraphenylsilanetetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic) dianhydride, m-phenylene-bis(triphenylphthalic) dianhydride, bis(triphenylphthalic)-4,4'-diphenyl ether dianhydride Examples of suitable dianhydrides include aromatic tetracarboxylic acid dianhydrides such as bis(triphenylphthalic)-4,4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalene succinic dianhydride, and 3,4-dicarboxy-1,2,3,4-tetrahydro-6-methyl-1-naphthalene succinic dianhydride. Among these, aromatic tetracarboxylic acid dianhydrides are preferred from the viewpoint of pigment adsorption.

[0046] The tetracarboxylic dianhydride is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. These may be used alone or in combination. Tetracarboxylic dianhydrides form a dispersing resin having two carboxyl groups per tetracarboxylic dianhydride unit by reacting with a hydroxyl group-containing compound, and are therefore preferred as components of the dispersing resin of the present invention from the viewpoint of pigment adsorption.

[0047] Examples of the tricarboxylic acid anhydride include aliphatic tricarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides.

[0048] Examples of the aliphatic tricarboxylic acid anhydride include 3-carboxymethylglutaric anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid-1,2-anhydride, and 1,3,4-cyclopentanetricarboxylic acid anhydride.

[0049] Examples of the aromatic tricarboxylic acid include benzenetricarboxylic anhydrides (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalenetricarboxylic anhydrides (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride, etc.), 3,4,4'-benzophenonetricarboxylic anhydride, 3,4,4'-biphenylethertricarboxylic anhydride, 3,4,4'-biphenyltricarboxylic anhydride, 2,3,2'-biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, and 3,4,4'-biphenylsulfonetricarboxylic anhydride. Among these, aromatic tricarboxylic anhydrides are preferred from the viewpoint of pigment adsorption.

[0050] The molar ratio of the acid anhydride groups in the one or more acid anhydrides selected from the tetracarboxylic acid anhydrides and tricarboxylic acid anhydrides to the hydroxyl groups in the hydroxyl group-containing compound is preferably acid anhydride groups / hydroxyl groups=0.5 to 1.5. Reaction at an appropriate ratio makes it easy to obtain a dispersion resin with good dispersibility.

[0051] The hydroxyl group-containing compound is preferably a monool or a polyol, such as a diol having a plurality of hydroxyl groups, among which the hydroxyl group in the polyol functions as a bonding point with the vinyl polymer moiety. Examples of polyols that serve as the bonding origin with the vinyl polymer moiety include at least one hydroxyl group-containing compound selected from the group consisting of compounds having two hydroxyl groups and one thiol group in the molecule and vinyl polymers containing a hydroxyl group at one end, such as 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin or 1-thioglycerol), 2-mercapto-1,2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl-2-methyl-1,3-propanediol, and 2-mercaptoethyl-2-ethyl-1,3-propanediol.

[0052] Examples of the dispersing resin (B1-1) having an acidic group include the following (B1-1-1) and (B1-1-2).

[0053] <Dispersion resin having acidic groups (B1-1-1)> The vinyl polymer portion of the dispersion resin (B1-1-1) having an acidic group is obtained by radical polymerization of (i) a monomer having at least one thermally crosslinkable group selected from the group consisting of a hydroxyl group, an oxetane group, a t-butyl group, and a blocked isocyanate group, (ii) a carboxyl group-containing monomer, and, if necessary, (iii) other monomers.

[0054] (i-1) [Hydroxyl group-containing monomer] The hydroxyl group-containing monomer is a (meth)acrylate monomer having a hydroxyl group, for example, a hydroxyalkyl (meth)acrylate such as 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4)-hydroxybutyl (meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate, and an alkyl-α-hydroxyalkyl acrylate such as ethyl-α-hydroxymethyl acrylate; or (meth)acrylamide monomers having a hydroxyl group, for example, N-(hydroxyalkyl)(meth)acrylamides such as N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, and N-(2-hydroxybutyl)(meth)acrylamide; Alternatively, a vinyl ether monomer having a hydroxyl group, for example, a hydroxyalkyl vinyl ether such as 2-hydroxyethyl vinyl ether, 2-(or 3-)hydroxypropyl vinyl ether, or 2-(or 3- or 4-)hydroxybutyl vinyl ether; Alternatively, an allyl ether monomer having a hydroxyl group, for example, a hydroxyalkyl allyl ether such as 2-hydroxyethyl allyl ether, 2-(or 3-)hydroxypropyl allyl ether, or 2-(or 3- or 4-)hydroxybutyl allyl ether, may be used.

[0055] Also preferred are monomers obtained by adding alkylene oxides and / or lactones to the above-mentioned hydroxyalkyl (meth)acrylates, alkyl-α-hydroxyalkyl acrylates, N-(hydroxyalkyl) (meth)acrylamides, hydroxyalkyl vinyl ethers, or hydroxyalkyl allyl ethers. Examples of the alkylene oxides to be added include ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3-, or 1,3-butylene oxide, and combinations of two or more of these. When two or more alkylene oxides are used in combination, the bonding form may be random and / or block. Examples of the lactones to be added include δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and combinations of two or more of these. Addition of both alkylene oxides and lactones is also acceptable.

[0056] (i-2) [Oxetane group-containing monomer] Examples of the oxetane group-containing monomer include (vinyloxyalkyl) alkyloxetane, (meth)acryloyloxyalkyloxetane, and [(meth)acryloyloxyalkyl] alkyloxetane. Among these, (3-ethyloxetan-3-yl)methyl methacrylate is preferred. An example of a commercially available product is ETERNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate) (manufactured by Ube Industries, Ltd.).

[0057] (i-3) [t-butyl group-containing monomer] Examples of the t-butyl group-containing monomer include t-butyl methacrylate and t-butyl acrylate.

[0058] (i-4) [Blocked isocyanate group-containing monomer] Examples of the blocked isocyanate group-containing monomer include 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate, etc. Commercially available products include Karenz MOI-BM (2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate) (manufactured by Showa Denko K.K.), Karenz MOI-BP (2-[(3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate) (manufactured by Showa Denko K.K.), etc.

[0059] The content of the oxetane group-containing monomer, t-butyl group-containing monomer, and blocked isocyanate group-containing monomer is preferably 5 to 90% by mass, more preferably 20 to 60% by mass, based on the total amount of monomers. If it is 5% by mass or more, it is possible to obtain a photosensitive coloring composition with excellent durability due to the effect of crosslinking, and if it is 90% by mass or less, the stability of the composition is also good, which is preferable.

[0060] (ii) [Carboxyl group-containing monomer] Examples of the carboxyl group-containing monomer include (meth)acrylic acid, crotonic acid, α-chloroacrylic acid, cinnamic acid, etc. Among these, (meth)acrylic acid is preferred because it has good copolymerizability and is easily available.

[0061] (iii) [Other monomers] In the vinyl polymer portion of the dispersing resin (B1-1-1) having an acidic group, other monomers than the thermally crosslinkable monomer and the carboxyl group-containing monomer can be used. Examples of other monomers include alkyl (meth)acrylates 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, lauryl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, and isobornyl (meth)acrylate; aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, and phenoxydiethylene glycol (meth)acrylate; heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate; alkoxypolyalkylene glycol (meth)acrylates such as methoxypolypropylene glycol (meth)acrylate and ethoxypolyethylene glycol (meth)acrylate; N-substituted (meth)acrylamides such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, and acryloylmorpholine; Amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate; and nitriles such as (meth)acrylonitrile.

[0062] Other examples include styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether and isobutyl vinyl ether; and vinyl fatty acids such as vinyl acetate and vinyl propionate.

[0063] <Dispersion resin having acidic groups (B1-1-2)> The dispersing resin (B1-1-2) having an acidic group has a polymerizable unsaturated group in the vinyl polymer portion.

[0064] The dispersing resin (B1-1-2) having an acidic group can be produced, for example, by reacting a compound having a (meth)acryloyl group, which is a polymerizable unsaturated group, and a functional group with a polymer of a monomer containing a functional group-containing monomer that reacts with the functional group. Examples include the product of glycidyl methacrylate and a polymer having a hydroxyl group or a carboxyl group, and the product of methacryloyloxyethyl isocyanate and a polymer having a hydroxyl group or a carboxyl group. The polymer having a hydroxyl group or a carboxyl group can be obtained by subjecting a polymer having a glycidyl group to a ring-opening reaction with an acid anhydride compound, or by subjecting a polymer having an acid anhydride group to a ring-opening reaction. For example, the dispersing resin described in JP 2011-157416 A can be mentioned.

[0065] [Dispersion resin (B1-2) having an acidic group] The dispersing resin (B1-2) having an acidic group is a dispersing resin represented by the following general formula (2), and specifically, is a dispersing resin described in JP-A-2007-140487.

[0066] General formula (2) (HOOC-) m -R 2 -(-COO-[-R 4 -COO-] n -R 5 ) t (In general formula (2), R 2 is a tetracarboxylic acid compound residue, R 5 is a monoalcohol residue, R 4 represents a lactone residue, m is 2 or 3, n is an integer of 1 to 50, and t is (4-m).

[0067] The acid value of the dispersing resin (B1) having an acidic group is preferably from 20 to 250 mgKOH / g, more preferably from 30 to 200 mgKOH / g, from the viewpoints of developability and pattern shape.

[0068] The dispersing resin (B1) having an acidic group can be used alone or in combination of two or more kinds.

[0069] The content of the dispersing resin (B1) having an acidic group is preferably from 3 to 200 parts by mass, more preferably from 5 to 100 parts by mass, relative to 100 parts by mass of the black colorant (A) from the viewpoints of developability and pattern shape.

[0070] (Other dispersing resins (B2)) The photosensitive coloring composition of the present invention can contain, as the dispersing resin (B), a dispersing resin (B2) other than the dispersing resin (B1) having an acidic group (hereinafter also referred to as other dispersing resin (B2)).

[0071] The other dispersing resin (B2) is not particularly limited, and known dispersing resins can be used. Among these, basic dispersing resins are preferred from the viewpoint of dispersion stability.

[0072] Examples of the basic group include a primary amino group, a secondary amino group, a tertiary amino group, a quaternary ammonium base, and a group containing a nitrogen atom such as a nitrogen-containing heterocycle.

[0073] Other dispersing resins (B2) include, for example, Disperbyk-2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, and 2164 manufactured by BYK Japan, SOLSPERSE-20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, and 76500 manufactured by The Lubrizol Japan Co., Ltd., and BASF Japan. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453 , 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc., and Ajisuper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno Co., Ltd. Further examples include dispersion resins described in JP 2004-182787 A, JP 2013-119568 A, JP 2017-019937 A, JP 2018-172530 A, etc.

[0074] [Polymerizable compound (C)] The photosensitive coloring composition of the present invention contains a polymerizable compound (C).

[0075] The polymerizable compound (C) may be a monomer or oligomer having a polymerizable unsaturated group, such as a vinyl group, a (meth)allyl group, or a (meth)acryloyl group.

[0076] (Polymerizable compound (C1) having a urethane bond) From the viewpoints of wrinkle suppression, pattern shape, and external light reflectivity, the photosensitive coloring composition of the present invention preferably contains a polymerizable compound (C1) having a urethane bond as the polymerizable compound (C). The polymerizable compound (C1) having a urethane bond forms a chemical crosslinked structure due to the reaction of polymerizable unsaturated groups in the coating, as well as a physical crosslinked structure due to intermolecular hydrogen bonds at the urethane bond sites. The molecular cohesive energy of the intermolecular hydrogen bonds at the urethane bond sites is greater than the cohesive energy of other organic structures such as ether bonds. Therefore, it is believed that a coating formed by curing a composition containing a polymerizable compound (C1) having a urethane bond is strengthened by the interaction between the urethane bonds, thereby suppressing chipping during development. Furthermore, the interaction between the urethane bonds has a weaker bonding strength than chemical bonds, providing adequate flexibility. It is believed that this contributes to the suppression of wrinkles.

[0077] Examples of the polymerizable compound (C1) having a urethane bond include urethane (meth)acrylates obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and urethane (meth)acrylates obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and further reacting the resulting mixture with a (meth)acrylate having a hydroxyl group.

[0078] Examples of the (meth)acrylate having a hydroxyl group include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy(meth)acrylate, and a hydroxyl group-containing polyol polyacrylate.

[0079] Examples of the polyfunctional isocyanate include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate; aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate; alicyclic diisocyanate such as isophorone diisocyanate; and biuret derivatives, isocyanate nurate derivatives, and trimethylolpropane adducts thereof.

[0080] The number of polymerizable unsaturated groups in the polymerizable compound (C1) having a urethane bond is preferably 3 to 15, more preferably 5 to 12, from the viewpoints of wrinkle prevention, pattern shape, and external light reflectivity.

[0081] The molecular weight of the polymerizable compound (C1) having a urethane bond is preferably from 500 to 5,000, more preferably from 500 to 3,000, from the viewpoints of wrinkle prevention, pattern shape, and external light reflectivity.

[0082] The polymerizable compound (C1) having a urethane bond can be used alone or in combination of two or more kinds.

[0083] From the viewpoints of wrinkle suppression, pattern shape, and external light reflectivity, the content of the polymerizable compound (C1) having a urethane bond is preferably 10% by mass or more, more preferably 20 to 80% by mass, and particularly preferably 30 to 60% by mass, based on 100% by mass of the polymerizable compound (C).

[0084] From the viewpoint of wrinkle suppression, the polymerizable compound (C1) having a urethane bond preferably contains one or more compounds selected from the group consisting of alicyclic urethane (meth)acrylates and aliphatic urethane (meth)acrylates, and more preferably contains an aliphatic urethane (meth)acrylate.

[0085] [Alicyclic urethane (meth)acrylate] The alicyclic urethane (meth)acrylate is not particularly limited, and a known compound can be used. For example, it can be obtained by using a polyfunctional isocyanate having an alicyclic structure in place of the polyfunctional isocyanate of the polymerizable compound (C1) having a urethane bond.

[0086] Examples of the polyfunctional isocyanate having an alicyclic structure include cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyl diisocyanate, methylcyclohexyl diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatemethyl)cyclohexane, methylcyclohexane diisocyanate, norbornane diisocyanate, bis(isocyanatemethyl)cyclohexane, etc. Further examples include biuret derivatives, isocyanate nurate derivatives, trimethylolpropane adducts, etc. of these compounds.

[0087] [Aliphatic urethane (meth)acrylate] The aliphatic urethane (meth)acrylate is not particularly limited, and known compounds can be used. For example, it can be obtained by changing the polyfunctional isocyanate having an alicyclic structure of the above-mentioned alicyclic urethane (meth)acrylate to a polyfunctional isocyanate having an aliphatic structure.

[0088] Examples of the polyfunctional isocyanate having an aliphatic structure include trimethylene diisocyanate, tetramethylene diisocyanate, hexamethylene diisocyanate, etc. Also included are biuret products, isocyanate nurate products, trimethylolpropane adduct products, etc.

[0089] The polymerizable compound (C1) having a urethane bond may have an acidic group from the viewpoint of developability. Examples of the acidic group include a sulfonic acid group, a carboxyl group, and a phosphate group. Among these, a carboxyl group is preferred.

[0090] The acidic group can be introduced into the polymerizable compound (C1) having a urethane bond by, for example, first reacting the (meth)acrylate having a hydroxyl group with the polyfunctional isocyanate, and then adding a mercapto compound having a carboxyl group to the reaction product.

[0091] Examples of the mercapto compound having a carboxyl group include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, o-mercaptobenzoic acid, 2-mercaptonicotinic acid, and mercaptosuccinic acid.

[0092] (Polymerizable compound (C2) having a 9,9-bisarylfluorene structure) From the viewpoint of wrinkle suppression and pattern shape, the photosensitive coloring composition of the present invention preferably contains a polymerizable compound (C2) having a 9,9-bisarylfluorene structure as the polymerizable compound (C). It is presumed that the 9,9-bisarylfluorene structure gives the coating film appropriate hardness and flexibility, making it possible to obtain a cured film that improves adhesion problems due to differences in the degree of curing between the surface and the interior of the film during curing, and wrinkles that occur during post-baking.

[0093] The glass transition temperature (hereinafter also referred to as Tg) of the polymerizable compound (C2) having a 9,9-bisarylfluorene structure is preferably 200°C or higher, more preferably 200 to 300°C, from the viewpoints of wrinkle prevention and pattern shape. The glass transition temperature can be measured by a known method, specifically, by the method described in Example 2 of JP-A-2009-173646.

[0094] The polymerizable compound (C2) having a 9,9-bisarylfluorene structure is preferably a compound represented by the following general formula (3) or general formula (4).

[0095] General formula (3) [ka] (In general formula (3), R1 and R3 each independently represent a hydrogen atom or a methyl group, R2 and R4 each independently represent an alkylene group, and p and q each independently represent an integer of 1 to 10.)

[0096] General formula (4) [ka] (In general formula (4), R5 and R7 each independently represent a hydrogen atom or a methyl group, R6 and R8 each independently represent an alkylene group, and x and y each independently represent an integer of 0 to 10. When x and y are 0, they represent a single bond.)

[0097] The polymerizable compound (C2) having a 9,9-bisarylfluorene structure is more preferably a compound represented by general formula (3) from the viewpoints of wrinkle prevention and pattern shape.

[0098] Specific examples of the compound represented by formula (3) or (4) are shown below, but the present invention is not limited to these.

[0099] [ka]

[0100] Chemical formula (9) [ka]

[0101] Commercially available polymerizable compounds (C2) having a 9,9-bisarylfluorene structure include OGSOL EA-0200, EA-0300, GA-5060P, and GA-2800 manufactured by Osaka Gas Chemicals Co., Ltd., and Miramer HR6060, HR6100, and HR6200 manufactured by Miwon Specialty Chemical Co., Ltd.

[0102] From the viewpoints of wrinkle suppression and pattern shape, the content of the polymerizable compound (C2) having a 9,9-bisarylfluorene structure is preferably 10% by mass or more, more preferably 20 to 80% by mass, and particularly preferably 30 to 60% by mass, based on 100% by mass of the polymerizable compound (C).

[0103] From the viewpoints of wrinkle suppression, pattern formation, and external light reflectivity, the photosensitive coloring composition of the present invention preferably contains, as the polymerizable compound (C), a polymerizable compound (C1) having a urethane bond and a polymerizable compound (C2) having a 9,9-bisarylfluorene structure.

[0104] The mass ratio of the polymerizable compound (C1) having a urethane bond to the polymerizable compound (C2) having a 9,9-bisarylfluorene structure is preferably 80:20 to 20:80, more preferably 70:30 to 30:70.

[0105] The total content of the polymerizable compound (C1) having a urethane bond and the polymerizable compound (C2) having a 9,9-bisarylfluorene structure is preferably 20% by mass or more, more preferably 40% by mass or more, and particularly preferably 60 to 90% by mass, based on 100% by mass of the polymerizable compound (C), from the viewpoints of wrinkle suppression, pattern formation, and external light reflectivity.

[0106] (Other polymerizable compounds (C3)) From the viewpoint of pattern shape, the photosensitive coloring composition of the present invention preferably contains a polymerizable compound (C3) other than the polymerizable compound (C1) having a urethane bond and the polymerizable compound (C2) having a 9,9-bisarylfluorene structure (hereinafter also referred to as other polymerizable compound (C3)).

[0107] Examples of other polymerizable compounds (C3) include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tricyclodecane di(meth)acrylate, Methanol di(meth)acrylate, ethoxylated bisphenol A di(meth)acrylate, 9,9-bis[4-(2-hydroxyethoxy)phenyl]fluorene diacrylate, 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 tetra(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, dipenta Examples include various acrylic acid esters and methacrylic acid esters such as erythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, (meth)acrylic acid ester of methylolated melamine, and epoxy(meth)acrylate, as well as styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, and acrylonitrile. Among these, compounds having 3 to 6 polymerizable unsaturated groups are preferred from the viewpoint of pattern shape.

[0108] Other commercially available polymerizable compounds (C3) include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-20, DPCA-30, DPCA-60, and DPCA-120 manufactured by Nippon Kayaku Co., Ltd., and Aronix M-303, M-305, M-306, M-309, M-310, M-321, and M-325 manufactured by Toagosei Co., Ltd. , M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M-406, M-450, M-452, M-408, M-211B, M-101A, M-5300, M-5400, M-5700, M-510, M-520, M-521, Viscoat #2500P manufactured by Osaka Organic Chemical Co., Ltd., and NK Ester ABE-300, A-DOG, A-DCP, A-BPE-4 manufactured by Shin-Nakamura Chemical Co., Ltd.

[0109] The other polymerizable compounds (C3) can be used alone or in combination of two or more.

[0110] The content of the polymerizable compound (C) is preferably from 1 to 60 mass %, more preferably from 2 to 50 mass %, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition.

[0111] [Photopolymerization initiator (D)] The photosensitive coloring composition of the present invention contains a compound (D1) represented by general formula (1) and an oxime-based photopolymerization initiator (D2) as the photopolymerization initiator (D). The photopolymerization initiator (D) is a compound that generates radicals by light and can initiate radical polymerization.

[0112] (Compound (D1) represented by general formula (1)) The photosensitive coloring composition of the present invention contains a compound (D1) represented by general formula (1).

[0113] General formula (1) [ka] (In general formula (1), R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. R3 represents a hydrogen atom or a monovalent substituent.)

[0114] R1 and R2 each independently represent a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. The alkyl group having 1 to 8 carbon atoms may be linear, branched, or cyclic, or may be a combination of these, and examples thereof include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, a pentyl group, an isopentyl group, a hexyl group, a heptyl group, an octyl group, a 2-ethylhexyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylmethyl group, etc. Among these, from the viewpoints of suppressing water stains and pattern shape, a linear alkyl group having 3 to 8 carbon atoms is preferred, and a linear alkyl group having 4 to 6 carbon atoms is more preferred.

[0115] R3 represents a hydrogen atom or any monovalent substituent. Examples of monovalent substituents include alkyl groups having 1 to 20 carbon atoms, such as methyl and ethyl; alkoxy groups having 1 to 20 carbon atoms, such as methoxy and ethoxy; halogen atoms, such as F, Cl, Br, and I; acyl groups having 1 to 20 carbon atoms; alkyl ester groups having 1 to 20 carbon atoms; alkoxycarbonyl groups having 1 to 20 carbon atoms; halogenated alkyl groups having 1 to 20 carbon atoms, aromatic ring groups having 4 to 20 carbon atoms; amino groups; aminoalkyl groups having 1 to 20 carbon atoms; hydroxyl groups; nitro groups; cyano groups; optionally substituted benzoyl groups; and optionally substituted thenoyl groups. Substituents that the benzoyl group or thenoyl group may have include alkyl groups having 1 to 10 carbon atoms, alkoxy groups having 1 to 10 carbon atoms, and alkoxycarbonyl groups having 1 to 10 carbon atoms. Among these, from the viewpoint of radical generation efficiency, a hydrogen atom and a nitro group are preferred, and a hydrogen atom is more preferred.

[0116] Examples of methods for producing the compound (D1) represented by general formula (1) include those described in JP-T-2019-507108 and JP-T-2019-528331.

[0117] Specific examples of the compound (D1) represented by general formula (1) are shown below, but the present invention is not limited to these.

[0118] [ka]

[0119] Among the compounds of chemical formulas (10) to (12), the compound of chemical formula (10) is preferred from the viewpoints of wrinkle suppression and pattern shape.

[0120] The compound (D1) represented by the general formula (1) can be used alone or in combination of two or more kinds.

[0121] (Oxime-based photopolymerization initiator (D2)) The photosensitive coloring composition of the present invention contains an oxime-based photopolymerization initiator (D2).

[0122] The oxime photopolymerization initiator (D2) is not particularly limited as long as it is a compound having an oxime group, and can use known compounds. Commercially available oxime photopolymerization initiator (D2) includes, for example, IRGACURE OXE-01, 02, 03 manufactured by BASF Japan, ADEKA Arklus N-1919 manufactured by ADEKA Corporation, TRONLY TR-PBG-301, 304, 305, 309, 314, 346, 358, 380, 365, 610, 3054, 3057 manufactured by Changzhou Strong New Materials Co., Ltd., OMNIRAD1312, 1314, 1316 manufactured by IGM Resins, SPI-02, 03, 04, 06, 07 manufactured by Samyang Corporation, DFI-020, 036, EOX-01 manufactured by Daito Chemistry Co., Ltd. Further examples include compounds described in JP 2005-215378 A, JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, JP 2011-105713 A, WO 2015 / 036910, JP 2021-011486 A, and the like.

[0123] Specific examples of the oxime-based photopolymerization initiator (D2) include the following, but the present invention is not limited thereto.

[0124] [ka]

[0125] [ka]

[0126] From the viewpoints of wrinkle suppression and pattern shape, the oxime photopolymerization initiator (D2) preferably contains one or more compounds selected from the group consisting of chemical formulas (13) to (20), and more preferably contains one or more compounds selected from the group consisting of chemical formulas (17), (19), and (20).

[0127] The oxime-based photopolymerization initiator (D2) can be used alone or in combination of two or more kinds.

[0128] The mass ratio of the compound (D1) represented by general formula (1) to the oxime-based photopolymerization initiator (D2) is preferably 90:10 to 10:90, more preferably 80:20 to 20:80, and particularly preferably 70:30 to 30:70, from the viewpoints of wrinkle suppression and pattern shape.

[0129] From the viewpoints of wrinkle suppression and pattern shape, the total content of the compound (D1) represented by general formula (1) and the oxime-based photopolymerization initiator (D2) is preferably 60 to 100 mass%, and more preferably 80 to 100 mass%, based on 100 mass% of the photopolymerization initiator (D).

[0130] (Other photopolymerization initiators (D3)) The photosensitive composition of the present invention can contain a compound (D1) represented by general formula (1) and a photopolymerization initiator (D3) other than the oxime-based photopolymerization initiator (D2) (hereinafter also referred to as other photopolymerization initiator (D3)).

[0131] The photopolymerization initiator (D3) is not particularly limited as long as it is a compound capable of initiating polymerization of the polymerizable compound (C) by light, and known photopolymerization initiators can be used. For example, acetophenone compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; triazine-based compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(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; acylphosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; Examples of the compound include quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds; carbazole compounds; imidazole compounds; and titanocene compounds.

[0132] The other photopolymerization initiators (D3) can be used alone or in combination of two or more.

[0133] The content of the photopolymerization initiator (D) is preferably 1 to 100 parts by mass, more preferably 3 to 50 parts by mass, and particularly preferably 5 to 30 parts by mass, relative to 100 parts by mass of the polymerizable compound (C) from the viewpoint of photocurability.

[0134] [Binder resin (E)] The photosensitive coloring composition of the present invention may contain a binder resin (E), which improves the heat resistance, chemical resistance, and other resistances of the cured film.

[0135] The binder resin (E) is not particularly limited, and known resins can be used.

[0136] The binder resin (E) can be classified into a non-photosensitive binder resin and a photosensitive binder resin, and from the viewpoint of developability, it is preferable that the binder resin (E) has an alkali-soluble group. Examples of the alkali-soluble group include a carboxyl group, a phosphate group, a sulfonic acid group, a hydroxyl group, and a phenolic hydroxyl group, and among these, a carboxyl group is preferred. The binder resin (E) may also contain a thermosetting group such as an epoxy group or an oxetanyl group.

[0137] (Non-photosensitive binder resin) Examples of the non-photosensitive binder resin include an acrylic resin having an acidic group, an α-olefin / maleic acid (anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth)acrylic acid copolymer, or an isobutylene / maleic acid (anhydride) copolymer. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferred.

[0138] (photosensitive binder resin) The photosensitive binder resin is a binder resin having a polymerizable unsaturated group. The photosensitive binder resin is preferably a resin synthesized by the following method (i) or (ii). When cured with active energy rays, the resin undergoes three-dimensional crosslinking, increasing the crosslink density and improving chemical resistance.

[0139] [Method (i)] In the method (i), for example, a polymer of an epoxy group-containing monomer and other monomers is first synthesized, and then a monocarboxyl group-containing monomer is added to the epoxy group of the polymer, and the resulting hydroxyl group is reacted with a polybasic acid anhydride to obtain a photosensitive binder resin.

[0140] 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.

[0141] Other monomers include, for example, 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, phenoxy (meth)acrylates such as diethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethylene oxide (EO)-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, EO-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, and PO-modified (meth)acrylate of nonylphenol; (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; styrene or styrenes such as α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether; vinyl fatty acid vinyl compounds such as vinyl acetate or vinyl propionate; Cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichloroethylene) N-substituted maleimides such as N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, and 9-maleimidoacridine; Examples include phosphate group-containing monomers such as 2-(meth)acryloyloxyethyl acid phosphate and compounds obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer described below with a phosphate esterifying agent such as phosphorus pentoxide or polyphosphoric acid.

[0142] Examples of the monocarboxyl group-containing monomer include monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid, and (meth)acrylic acid substituted with haloalkyl, alkoxyl, halogen, nitro, or cyano at the α-position.

[0143] Examples of polybasic acid anhydrides include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, etc. If necessary, the remaining anhydride groups can be hydrolyzed using a tricarboxylic acid dianhydride such as trimellitic anhydride or a tetracarboxylic acid dianhydride such as pyromellitic anhydride.

[0144] Another method similar to method (i) is to synthesize a polymer of a carboxyl group-containing monomer and other monomers, and then add an epoxy group-containing monomer to some of the carboxyl groups of the polymer to obtain a photosensitive binder resin.

[0145] [Method (ii)] In the method (ii), for example, a polymer of a hydroxyl group-containing monomer, a monocarboxyl group-containing monomer, and other monomers is synthesized, and then the hydroxyl group of the polymer is reacted with the isocyanate group of an isocyanate group-containing monomer.

[0146] Examples of hydroxyl group-containing monomers include hydroxyalkyl methacrylates such as 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3-, or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Other examples include polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to a hydroxyalkyl (meth)acrylate, and polyester mono(meth)acrylates obtained by addition polymerization of poly(γ-valerolactone), poly(ε-caprolactone), and / or poly(12-hydroxystearic acid). Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred in terms of their resistance to foreign matter formation in the coating. Furthermore, glycerol mono(meth)acrylate is preferred in terms of photosensitivity.

[0147] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0148] The monocarboxyl group-containing monomer and other monomers that can be used are those described above.

[0149] The raw materials used in the synthesis of the photosensitive binder resin can be used either alone or in combination of two or more kinds.

[0150] The binder resin (E) can be used alone or in combination of two or more kinds.

[0151] From the viewpoint of developability, the weight average molecular weight (Mw) of the binder resin (E) is preferably 2,000 to 40,000, more preferably 3,000 to 30,000, and particularly preferably 4,000 to 20,000. The value of Mw / Mn (number average molecular weight) is preferably 10 or less. An appropriate weight average molecular weight (Mw) improves adhesion to the substrate and developability.

[0152] The acid value of the binder resin (E) is preferably 30 to 200 mgKOH / g, more preferably 40 to 180 mgKOH / g. A suitable acid value improves the adhesion to the substrate and the developability.

[0153] The content of the binder resin (E) is preferably from 20 to 400 parts by mass, more preferably from 50 to 250 parts by mass, relative to 100 parts by mass of the black colorant (A).

[0154] (Binder resin (E1)) From the viewpoint of suppressing wrinkles, the photosensitive coloring composition of the present invention preferably contains, as the binder resin (E), a binder resin (E1) having a monomer unit (e1) represented by the following structure.

[0155] [ka] (R1 represents a hydrogen atom or a methyl group. R2 represents an alkylene group having 2 or 3 carbon atoms. R3 represents a hydrogen atom or an alkyl group having 1 to 20 carbon atoms which may have a benzene ring. n represents an integer of 1 to 15. When n is 2 or greater, multiple R2s may be the same or different.)

[0156] Examples of the monomer forming the monomer unit (e1) include ethylene oxide (EO)-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO- or PO-modified (meth)acrylate of nonylphenol, etc. Among these, EO- or PO-modified (meth)acrylate of paracumylphenol is preferred from the viewpoint of wrinkle suppression.

[0157] The content of the monomer unit (e1) is preferably 10 to 60 mass % in 100 mass % of all the structural units of the binder resin (E1).

[0158] The monomer units (e2) other than the monomer units (e1) constituting the binder resin (E1) (also referred to as other monomer units (e2)) are not particularly limited as long as they are formed from a monomer copolymerizable with the monomer forming the monomer unit (e1), and can be formed using known monomers. For example, they can be formed from the above-mentioned monocarboxyl group-containing monomers, hydroxyl group-containing monomers, epoxy group-containing monomers, and other monomers.

[0159] The content of the binder resin (E1) is preferably 10% by mass or more, more preferably 20% by mass or more, and particularly preferably 40 to 100% by mass, based on 100% by mass of the binder resin (E).

[0160] [Dye derivative (F)] The photosensitive coloring composition of the present invention may contain a dye derivative (F).

[0161] The dye derivative (F) is not particularly limited, and examples thereof include dye derivatives having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. Examples of the dye derivative (F) include compounds having an acidic substituent such as a sulfo group, a carboxy group, or a phosphate group, and amine salts thereof, compounds having a basic substituent such as a sulfonamide group or a terminal tertiary amino group, and compounds having a neutral substituent such as a phenyl group or a phthalimidoalkyl group. Examples of organic pigments include diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, indole pigments such as benzoisoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

[0162] Specifically, diketopyrrolopyrrole dye derivatives are disclosed in JP 2001-220520 A, WO 2009 / 081930 A, WO 2011 / 052617 A, WO 2012 / 102399 A, and JP 2017-156397 A; phthalocyanine dye derivatives are disclosed in JP 2007-226161 A, WO 2016 / 163351 A, JP 2017-165820 A, and Japanese Patent No. 5753266 A; and anthraquinone dye derivatives are disclosed in JP 63-264 A. 674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO 2009 / 025325, as quinacridone dye derivatives, JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383, as dioxazine dye derivatives, JP-A-2011-162662, as thiazine indigo dye derivatives, JP-A-2007-314785, as triazine Examples of benzoisoindole dye derivatives include those disclosed in JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, and JP-A-2007-314681; examples of benzoisoindole dye derivatives include those disclosed in JP-A-2009-57478; and examples of quinophthalone dye derivatives include those disclosed in JP-A-2003-167112, JP-A-2006-291194, JP-A-2008-31281, and JP-A-2012-226 Examples of naphthol-based dye derivatives include those described in JP-A-2012-208329 and JP-A-2014-5439; examples of azo-based dye derivatives include those described in JP-A-2001-172520 and JP-A-2012-172092; examples of acidic substituents include those described in JP-A-2004-307854; and examples of basic substituents include those known in JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404, etc.In these documents, the dye derivative is sometimes referred to as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound, but the compound having a substituent such as an acidic group, a basic group, or a neutral group in the organic dye residue is synonymous with the dye derivative.

[0163] The dye derivative (F) can be used alone or in combination of two or more kinds.

[0164] The content of the dye derivative (F) is preferably from 1 to 20 parts by mass, more preferably from 2 to 10 parts by mass, relative to 100 parts by mass of the black colorant (A).

[0165] [Sensitizer (G)] The photosensitive coloring composition of the present invention can contain a sensitizer (G).

[0166] Examples of the sensitizer (G) include polymethine dyes such as chalcone derivatives, unsaturated ketones typified by dibenzalacetone, 1,2-diketone derivatives typified by benzil and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and 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, and tetrapyrazinoporphyra. Examples of suitable ruthenium compounds include ruthenium ether derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, Michler's ketone derivatives, α-acyloxy esters, acyl oxides, methylphenyl glyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4′-diethylisophthalophenone, 3,3′ or 4,4′-tetra(t-butylperoxycarbonyl)benzophenone, and 4,4′-bis(diethylamino)benzophenone.

[0167] Among the sensitizers (G), thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred. Specific examples of preferred compounds include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole.

[0168] The sensitizer (G) can be used alone or in combination of two or more kinds.

[0169] The content of the sensitizer (G) 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 (D). When an appropriate amount is contained, photocurability and developability are improved.

[0170] [Thermosetting compound (H)] The photosensitive coloring composition of the present invention can contain a thermosetting compound (H), which reacts in the heating step to increase the crosslink density and improve the heat resistance.

[0171] The thermosetting compound (H) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (H) include epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenol compounds. Among these, epoxy compounds and oxetane compounds are preferred.

[0172] (Epoxy compound (H1)) Examples of the epoxy compound (H1) include polycondensates of bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), polycondensates of phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene, alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, etc.), and polycondensates of phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, etc.). Examples of suitable epoxy resins include polymers of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), polycondensates of phenols and aromatic dimethanols (benzenedimethanol, α,α,α',α'-benzenedimethanol, biphenyldimethanol, α,α,α',α'-biphenyldimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α,α'-dichloroxylene, bischloromethylbiphenyl, etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidylamine epoxy resins, and glycidyl ester epoxy resins.

[0173] Commercially available products include, for example, Epicoat 807, 815, 825, 827, 828, 190P, and 191P manufactured by Yuka Shell Epoxy Co., Ltd., and TECHMORE manufactured by Mitsui Chemicals, Inc. VG3101L, EPPN-201, 501H, 502H, EOCN-102S, 103S, 104S, 1020 manufactured by Nippon Kayaku Co., Ltd., Epicoat 1004, 1256, JER1032H60, 157S65, 157S70, 152, 154 manufactured by Japan Epoxy Resins Co., Ltd., Celloxide 2021, EHPE-3150 manufactured by Daicel Chemical Industries, Ltd., Denacol EX-211, 212, 252, 313, 314, 321, 411, 421, 512, 521, 611, 612, 614, 614B, 622, 711, 721 manufactured by Nagase ChemteX Corporation, TEPIC-L, H, S manufactured by Nissan Chemical Industries, Ltd., and the like.

[0174] From the viewpoint of heat resistance of the cured film, the content of the epoxy compound (H1) is preferably from 0.5 to 50 mass %, more preferably from 1 to 40 mass %, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition.

[0175] (Oxetane Compound (H2)) The oxetane compound (H2) is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher functional oxetane compounds.

[0176] Examples of monofunctional oxetane compounds 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, and 3-ethyl-3-{[3-(triethoxysilyl)propoxy]methyl}oxetane.

[0177] Examples of commercially available products include OXE-10,30 manufactured by Osaka Organic Chemical Industry Co., Ltd. and OXT-101,212 manufactured by Toagosei Co., Ltd.

[0178] Examples of the bifunctional oxetane compound include 4,4'-bis[(3-ethyl-3-oxetanyl)methoxymethyl]biphenyl), 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 1,4-bis{[(3-ethyl-3-oxetanyl)methoxy]methyl}benzene, di[1-ethyl(3-oxetanyl)]methyl ether, di[1-ethyl(3-oxetanyl)]methyl ether 3-ethyl-3-hydroxymethyloxetane, 3- Ethyl-3-(2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(2-phenoxymethyl)oxetane, 3,7-bis(3-oxetanyl)-5-oxa-nonane, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl]ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl]propane, ethyleneglycol bis(3-ethyl-3-oxetanylmethyl)ether, dicyclopentenylbis(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.

[0179] Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0180] Examples of trifunctional or higher oxetane compounds 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, and caprolactone-modified dipentaerythritol. Examples of such polymers include erythritol 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, the oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462), and polymers obtained by radical polymerization of (meth)acrylic monomers such as the above-mentioned OXE-30.

[0181] From the viewpoint of heat resistance of the cured film, the content of the oxetane compound (H2) is preferably from 0.5 to 50 mass %, more preferably from 1 to 40 mass %, in 100 mass % of the nonvolatile content of the photosensitive coloring composition.

[0182] The melamine compound is a compound having a melamine ring structure. The melamine compound is preferably a methylol or ether type compound, and more preferably a melamine compound having an average of 5.0 or more methylol groups and / or ether groups per melamine ring. Having an appropriate number of methylol groups or ether groups makes it easier to obtain just the right amount of heat resistance.

[0183] Examples of commercially available products include Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MS-001, MX-002, MX-730, MX-750, MX-708, MX-706, MX-042, MX-45, MX-500, MX-520, MX-43, MX-417, and MX-410 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 manufactured by Nippon Cytec Industries Co., Ltd.

[0184] Among these, Nikalac MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, and MX-45 manufactured by Sanwa Chemical Co., Ltd., and Cymel 232, 235, 236, 238, 300, 301, 303, and 350 manufactured by Nippon Cytec Industries Co., Ltd., which have an average of 5.0 or more methylol groups and / or ether groups per melamine ring, are preferred in terms of increasing crosslink density.

[0185] The thermosetting compound (H) can be used alone or in combination of two or more kinds.

[0186] [Curing agent (curing accelerator)] The photosensitive coloring composition of the present invention can be used in combination with a curing agent (curing accelerator) to aid in the curing of the thermosetting compound (H). Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. Examples of the curing agent include amine compounds (e.g., dicyandiamide, benzyldimethylamine, 4-(dimethylamino)-N,N-dimethylbenzylamine, 4-methoxy-N,N-dimethylbenzylamine, 4-methyl-N,N-dimethylbenzylamine, etc.), quaternary ammonium salt compounds (e.g., triethylbenzylammonium chloride, etc.), blocked isocyanate compounds (e.g., dimethylamine, etc.), imidazole derivative bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, Examples of suitable amines include 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc., phosphorus compounds (e.g., triphenylphosphine, etc.), and S-triazine derivatives (e.g., 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino-S-triazine, 2-vinyl-4,6-diamino-S-triazine-isocyanuric acid adduct, 2,4-diamino-6-methacryloyloxyethyl-S-triazine-isocyanuric acid adduct, etc.).

[0187] The curing agents can be used alone or in combination of two or more.

[0188] The content of the curing agent is preferably 0.01 to 15 parts by mass relative to 100 parts by mass of the thermosetting compound (H).

[0189] [Thiol-based chain transfer agents (I)] The photosensitive coloring composition of the present invention can contain a thiol-based chain transfer agent (I). When the thiol-based chain transfer agent (I) is used in combination with a photopolymerization initiator (D), a thiyl radical that is resistant to polymerization inhibition by oxygen is generated during radical polymerization after light irradiation, thereby improving the photosensitivity of the photosensitive coloring composition.

[0190] The thiol chain transfer agent (I) is preferably a polyfunctional thiol having two or more thiol groups (SH groups), more preferably a polyfunctional thiol having four or more thiol groups. As the number of functional groups increases, photocuring becomes easier from the surface to the deepest part of the film.

[0191] Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthioglycolate, Examples of the thiopropionate include erythritol tetrakisthiopropionate, trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. Preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

[0192] The thiol chain transfer agent (I) can be used alone or in combination of two or more kinds.

[0193] The content of the thiol chain transfer agent (I) is preferably 1 to 10 mass %, more preferably 2 to 8 mass %, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, photosensitivity is improved and wrinkles are less likely to occur on the surface of the cured film.

[0194] [Polymerization inhibitor (J)] The photosensitive coloring composition of the present invention may contain a polymerization inhibitor (J).

[0195] Examples of the polymerization inhibitor (J) include alkyl catechol compounds such as catechol, resorcinol, 1,4-hydroquinone, 2-methyl catechol, 3-methyl catechol, 4-methyl catechol, 2-ethyl catechol, 3-ethyl catechol, 4-ethyl catechol, 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-t-butyl catechol, 3-t-butyl catechol, 4-t-butyl catechol, and 3,5-di-t-butyl catechol; 2-methyl resorcinol, 4-methyl resorcinol, 2-ethyl resorcinol, 4-ethyl resorcinol, 2-propyl resorcinol, 4-propyl resorcinol; alkylresorcinol compounds such as 4-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, and 4-t-butylresorcinol; alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, and 2,5-di-t-butylhydroquinone; phosphine compounds such as tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, and tribenzylphosphine; phosphine oxide compounds such as trioctylphosphine oxide and triphenylphosphine oxide; phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite; pyrogallol; and phloroglucin.

[0196] The content of the polymerization inhibitor (J) is preferably 0.01 to 0.4% by mass in 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0197] [Ultraviolet absorber (K)] The photosensitive coloring composition of the present invention may contain an ultraviolet absorber (K).

[0198] The ultraviolet absorber (K) is an organic compound having an ultraviolet absorbing function, and examples thereof include benzotriazole-based organic compounds, triazine-based organic compounds, benzophenone-based organic compounds, salicylic acid ester-based organic compounds, cyanoacrylate-based organic compounds, and salicylate-based organic compounds.

[0199] 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, 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 mixture, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3-(2H-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate / polyethylene glycol 300 reaction products, 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 octyl-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, and 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate.

[0200] Examples of commercially available products include TINUVIN P, PS, 234, 326, 329, 384-2, 900, 928, 99-2, and 1130 manufactured by BASF Japan Ltd., ADK STAB LA-29, LA-31RG, LA-32, and LA-36 manufactured by ADEKA Corporation, KEMISORB71, 73, 74, 79, and 279 manufactured by Chemipro Chemical Co., Ltd., and RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

[0201] Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4,6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, and the reaction product of 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine with (2-ethylhexyl)-glycidic acid ester. Examples of such compounds include 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, and 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

[0202] Examples of commercially available products include KEMISORB 102 manufactured by Chemipro Chemicals, TINUVIN 400, 405, 460, 477, 479, and 1577ED manufactured by BASF Japan, Adekastab LA-46 and LA-F70 manufactured by ADEKA, and CYASORB UV-1164 manufactured by Sun Chemical.

[0203] Examples of benzophenone compounds include 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3-oxide, 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, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

[0204] Examples of commercially available products include KEMISORB 10, 11, 11S, 12, and 111 manufactured by Chemipro Chemicals, SEESORB 101 and 107 manufactured by Shipro Chemicals, Adekastab 1413 manufactured by ADEKA, and UV-12 manufactured by Sun Chemical.

[0205] Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0206] The content of the ultraviolet absorber (K) is preferably 5 to 70% by mass relative to 100% by mass of the total of the photopolymerization initiator (D) and the ultraviolet absorber (K).

[0207] [Antioxidant (L)] The photosensitive coloring composition of the present invention can contain an antioxidant (L). The antioxidant (L) prevents yellowing of the photopolymerization initiator (D) and thermosetting compound (H) in the photosensitive coloring composition due to oxidation during the thermal process of thermal curing or ITO annealing. In particular, when the concentration of the black colorant (A) in the photosensitive coloring composition is high, the content of the polymerizable compound (C) is relatively reduced, and if the amount of the photopolymerization initiator (D) is increased or a thermosetting compound is added to address this, the cured film is likely to yellow. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented. The antioxidant (L) is preferably a compound that does not contain a halogen atom.

[0208] Examples of the antioxidant (L) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds, etc. Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0209] Examples of hindered phenol antioxidants include 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2-t-butyl-5-methylphenol), 3-(3,5-di-t-butyl-4-hydroxyphenyl)stearyl propionate, pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8,10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2'-methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di -t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis(3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis(dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4 ,6-bis(octylthiomethyl)-o-cresol, bis[3-(3-methyl-4-hydroxy-5-t-butylphenyl)propionic acid]ethylenebisoxybisethylene, 1,6-hexanediol bis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 2,4-bis-(n-octylthio)-6-(4-hydroxy-3,5-di-t-butylanilino)-1,3,5-triazine, Examples include 2,2'-thio-bis-(6-t-butyl-4-methylphenol), 2,5-di-t-amyl-hydroquinone, 2,6-di-t-butyl-4-nonylphenol, 2,2'-isobutylidene-bis-(4,6-dimethyl-phenol), 2,2'-methylene-bis-(6-(1-methyl-cyclohexyl)-p-cresol), and 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol.

[0210] Examples of commercially available products include ADK STAB AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, and AO-330 manufactured by ADEKA Corporation, KEMINOX 101, 179, 76, and 9425 manufactured by Chemipro Corporation, IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, and 565 manufactured by BASF Japan Ltd., and Cyanox CY-1790 and CY-2777 manufactured by Sun Chemical Company.

[0211] Examples of the hindered amine antioxidant include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6-tetramethyl-4-piperidyl)1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl)sebacate, bis(2,2,6,6-tetramethyl-4-piperidyl)sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl tetramethyl-4-piperidyl methacrylate, 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1- Ester of piperidineethanol and 3,5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl)amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, decanedioic acid bis(2,2,6,6-tetramethyl-1-(octyloxy)-4-piperidinyl) ester, reaction products of 1,1-dimethylethyl hydroperoxide with octane, bis(1,2,2,6,6-pentamethyl-4-pyridyl)[[3,5-bi N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,2,6,6-tetramethyl-4-piperidyl ...Examples include 6-hexamethylenediamine and 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide.

[0212] Examples of commercially available products include ADK STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87, LA-402F, and LA-502XP manufactured by ADEKA CORPORATION; KAMISTAB 29, 62, 77, and 94 manufactured by Chemipro Chemicals; Tinuvin 111FDL, 123, 144, 249, 292, and 5100 manufactured by BASF Japan; and Cyasorb UV-3346, UV-3529, and UV-3853 manufactured by Sun Chemical Company.

[0213] Examples of phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis(4,6-di-t-butylphenyl)2-ethylhexyl phosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12 to C15 alkyl)-4,4'-isopropylidene diphenyl diphosphite, diphenyl mono (2-ethylhexyl) phosphite, diphenyl isodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)-4,4-biphenyl diphosphonate, tris(tridecyl) phosphite, phenyl isooctyl phosphite, phenyl isodecyl phosphite, phenyl di(tridecyl) phosphite, diphenyl isooctyl phosphite, diphenyl tridecyl phosphite, 4,4'-isopropylidene Diphenyl alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di(nonylphenyl)pentaerythritol diphosphite, phenyl bisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl Examples include 1,1,3-tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzyl phosphite diethyl ester, sodium bis(4-t-butylphenyl)phosphite, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, and ethyl bis(2,4-di-t-butyl-6-methylphenyl)phosphite.

[0214] Examples of commercially available products include Adeka Stab PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, and TPP manufactured by ADEKA Corporation, IRGAFOS168 manufactured by BASF Japan, and HostanoxP-EPQ manufactured by Clariant Chemicals.

[0215] Examples of sulfur-based antioxidants include 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], ditridecyl 3,3'-thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o-cresol, and 2,4-bis[(laurylthio)methyl]-o-cresol.

[0216] Examples of commercially available products include Adekastab AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0217] The antioxidant (L) can be used alone or in combination of two or more kinds.

[0218] The content of the antioxidant (L) is preferably 0.5 to 5.0% by mass relative to 100% by mass of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the transmittance, spectral characteristics, and sensitivity are improved.

[0219] [Leveling agent (M)] The photosensitive coloring composition of the present invention can contain a leveling agent (M). This improves the wettability and drying properties of the composition to the substrate during application. Examples of the leveling agent (M) include silicone surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0220] Examples of silicone surfactants include linear polymers formed from siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0221] Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, 378, 3455, UV3510, and 3570 manufactured by BYK-Chemie Co., Ltd., and FZ-7002 and 211 manufactured by Dow Corning Toray Co., Ltd. 0, 2122, 2123, 2191, 5609, and X-22-4952, X-22-4272, X-22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, and KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

[0222] Examples of the fluorine-based surfactant include a surfactant or leveling agent having a fluorocarbon chain.

[0223] Examples of commercially available products include Surflon S-242, 243, 420, 611, 651, and 386 manufactured by AGC Seimi Chemical Co., Ltd.; Megafac F-253, 477, 551, 552, 555, 558, 560, 570, 575, and 576, R-40-LM, R-41, RS-72-K, and DS-21 manufactured by DIC Corporation; FC-4430 and 4432 manufactured by Sumitomo 3M Limited; EF-PP31N09, EF-PP33G1, and EF-PP32C1 manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.; and Futergent 602A manufactured by Neos Corporation.

[0224] Examples of nonionic surfactants include polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myrister ether, polyoxyethylene octyldodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrenated phenyl ether, polyoxyethylene tribenzyl phenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, and sorbitan tristearate. sorbitan monooleate, sorbitan trioleate, sorbitan sesquioleate, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxyethylene sorbitan tetraoleate, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl alkanolamide, alkyl imidazoline, and the like.

[0225] Commercially available products include, for example, Emulgen 103, 104P, 106, 108, 109P, 120, 123P, 130K, 147, 150, 210P, 220, 306P, 320P, 350, 404, 408, 409PV, 420, 430, 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, and L manufactured by Kao Corporation. S-110, LS-114, MS-110, A-60, A-90, B-66, PP-290, Latemul PD-420, PD-430, PD-430S, PD-450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V, SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW- L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60(K), Amit 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Pluronic (registered trademark) L-23, 31, 44, 61, 62, 64, 71, 72, 101, 121, TR-701, 702, 704, 913R manufactured by ADEKA Corporation, and (meth)acrylic acid (co)polymer Polyflow No. 75, No. 90, No. 95 manufactured by Kyoeisha Chemical Co., Ltd.

[0226] Examples of cationic surfactants include alkylamine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

[0227] Examples of commercially available products include Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate, manufactured by Kao Corporation.

[0228] Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonate, sodium alkyldiphenyletherdisulfonate, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphates.

[0229] Examples of commercially available products include Futergent 100 and 150 manufactured by Neos Corporation, and Adeka Hope YES-25, Adekacol TS-230E, PS-440E, and EC-8600 manufactured by ADEKA Corporation.

[0230] Examples of amphoteric surfactants include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine; and alkylamine oxides such as lauryldimethylamine oxide.

[0231] Commercially available products include Anhithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N manufactured by Kao Corporation.

[0232] The leveling agent (M) can be used alone or in combination of two or more kinds.

[0233] The content of the leveling agent (M) is preferably 0.001 to 2.0 mass%, more preferably 0.005 to 1.0 mass%, based on 100 mass% of the nonvolatile content of the photosensitive coloring composition. When an appropriate amount is contained, the balance between the coatability and adhesion of the photosensitive coloring composition is further improved.

[0234] [Storage stabilizer (N)] The photosensitive coloring composition of the present invention can contain a storage stabilizer (N). This stabilizes the viscosity of the photosensitive coloring composition over time. Examples of the storage stabilizer (N) include quaternary ammonium chlorides such as benzyl trimethyl 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.

[0235] The content of the storage stabilizer (N) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the black colorant (A).

[0236] [Adhesion improver (O)] The photosensitive coloring composition of the present invention may contain an adhesion improver (O), which improves the adhesion between the cured film and the substrate and also makes it easier to form narrow patterns by photolithography.

[0237] Examples of the adhesion improver (O) include silane coupling agents. Examples of the silane coupling agent include 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, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl) silane coupling agents such as aminosilanes such as 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride; mercapto compounds such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryl compounds such as p-styryltrimethoxysilane; ureido compounds such as 3-ureidopropyltriethoxysilane; sulfides such as bis(triethoxysilylpropyl)tetrasulfide; and isocyanates such as 3-isocyanatepropyltriethoxysilane.

[0238] The adhesion improver (O) can be used alone or in combination of two or more kinds.

[0239] The content of the adhesion improver (O) is preferably from 0.01 to 10 parts by mass, more preferably from 0.05 to 5 parts by mass, relative to 100 parts by mass of the black colorant (A).

[0240] [Organic solvent (P)] The photosensitive coloring composition of the present invention may contain an organic solvent (P).

[0241] Examples of the organic solvent (P) include 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy- 3-Methylbutyl acetate, 3-methoxybutanol, 3-methoxybutyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyro Lactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether,Examples of the alkyl esters include dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, and dibasic acid esters. Among these, from the viewpoints of pigment dispersibility and alkali-soluble resin solubility, glycol acetates such as ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate, alcohols such as benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.

[0242] The organic solvent (P) can be used alone or in combination of two or more kinds.

[0243] [Method for producing photosensitive coloring composition] The photosensitive coloring composition of the present invention can be produced by dispersing a black colorant (A), a dispersing resin (B), a dye derivative (F), an organic solvent (P), and the like to produce a dispersion. The dispersion can then be mixed with a polymerizable compound (C), a photopolymerization initiator (D), a binder resin (E), and the like. The timing of blending each material is optional. The dispersion process can also be performed multiple times.

[0244] Examples of dispersing machines for carrying out the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

[0245] The average dispersed particle size (secondary particle size) of the pigment in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. If the particle size is appropriate, a photosensitive coloring composition with high dispersion stability is easily obtained.

[0246] The average dispersed particle size (secondary particle size) is measured using, for example, Nikkiso's Microtrac UPA-EX150, which employs dynamic light scattering (FFT power spectrum method), with particle permeability set to absorption mode, particle shape set to non-spherical, and the D50 particle size set to the average size. The dilution solvent used for measurement is the same organic solvent used for dispersion, and it is preferable to measure samples treated with ultrasound immediately after sample preparation, as this tends to provide results with little variation.

[0247] The photosensitive coloring composition is preferably subjected to centrifugation, filtration using a sintered filter or a membrane filter, etc., to remove coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably coarse particles of 0.5 μm or more, and dust particles mixed in. The photosensitive coloring composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

[0248] <Cured film> The cured film of the present invention can be obtained by curing a film formed using the photosensitive coloring composition of the present invention through a treatment such as exposure to light, etc. The cured film may be a patterned cured film.

[0249] [Method of manufacturing the cured film] The method for producing the cured film is not particularly limited, and for example, the cured film can be produced by carrying out the following steps: step (1) of applying a photosensitive coloring composition onto a substrate to form a layer (coating) of the composition; step (2) of exposing the layer to light in a pattern through a mask; step (3) of developing the unexposed parts with an alkali to form a patterned cured film; and step (4) of heat-treating (post-baking) the pattern.

[0250] The method for producing the cured film will be described in detail below. (Process (1)) In the step (1) of forming a composition layer, the photosensitive coloring composition is applied onto a substrate by a method such as spin coating, roll coating, slit coating, casting coating, or inkjet coating, and then dried (pre-baked) at a temperature of 50 to 120°C for 10 to 120 seconds using an oven, a hot plate, or the like, as needed. Examples of the substrate include a glass substrate and a silicon substrate. The silicon substrate may have an imaging element such as a CCD or a CMOS formed on its surface. If necessary, an undercoat layer may be provided on the substrate to improve adhesion with upper layers, prevent diffusion of substances, and flatten the substrate surface. The coating is preferably carried out so that the layer has a thickness of 0.05 to 10.0 μm after drying, and more preferably 0.3 to 5 μm.

[0251] (Process (2)) In the exposure step, the layer obtained in step (1) is exposed to light in a specific pattern through a mask using an exposure device such as a stepper, thereby obtaining a cured film. Examples of radiation used for exposure include ultraviolet rays such as g-rays, h-rays, and i-rays.

[0252] (Step (3)) The cured film obtained in step (2) is subjected to an alkali development treatment, whereby the composition layer in the unexposed areas is dissolved in an alkaline aqueous solution, leaving only the cured areas, thereby obtaining a patterned cured film. Examples of the developer include alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene. The concentration of the developer is preferably from 0.001 to 10% by mass, more preferably from 0.01 to 1% by mass. The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, it suppresses pattern roughening and peeling, and improves the remaining film rate after development.

[0253] Examples of the developing method include a dipping method, a spraying method, a puddling method, etc. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water.

[0254] (Step (4)) The heat treatment (post-baking) is performed by heating the patterned cured film obtained in step (3) to sufficiently cure it. The heating temperature for post-baking is preferably 100 to 300° C., more preferably 150 to 250° C. The heating time is preferably about 2 minutes to 1 hour, more preferably about 3 minutes to 30 minutes.

[0255] [Properties of cured film] From the viewpoint of light-shielding properties, the cured film obtained by curing the photosensitive coloring composition of the present invention preferably has an optical density (hereinafter also referred to as OD value) at a film thickness of 2.0 μm of 1.8 or more, more preferably 1.9 or more, and particularly preferably 2.0 or more. The upper limit is not particularly limited, but is preferably 10 or less.

[0256] The method for measuring the thickness of the cured film is as follows.

[0257] (Film thickness measurement) The photosensitive coloring composition of the present invention was applied to a glass substrate by spin coating so that the film thickness after drying was 2.0 μm, and after drying on a hot plate at 70 ° C for 1 minute, the entire surface was exposed to light using an ultra-high pressure mercury lamp. After that, the substrate was spray-developed using an alkaline developer at 23 ° C, washed with ion-exchanged water, air-dried, and heated (post-baked) in a clean oven at 230 ° C for 30 minutes to obtain a cured film. The obtained cured film was measured at five random locations using Dektak 3030 (manufactured by Nippon Shinku Gijutsu Co., Ltd.), and the average value was taken as the film thickness. The above-mentioned film thickness of 2.0 μm includes the range of tolerance allowed in the technical field to which the present invention pertains, specifically, the film thickness is within the range of 2.0 μm±0.2 μm.

[0258] (Optical density measurement) The cured film whose thickness had been measured was measured at five randomly selected points using a Macbeth densitometer (GretagMacbeth D200-II), and the average value was taken as the optical density.

[0259] <Light-blocking filter> The cured film of the present invention can be used for a light-shielding filter. The cured film prepared using the photosensitive coloring composition of the present invention has excellent light-shielding properties as described above. The light-shielding filter of the present invention can be produced by the same method as the above-mentioned cured film.

[0260] <Color filter> The cured film of the present invention can be used in a color filter. The form in which it is used in a color filter is not particularly limited, but it is preferably used as a black matrix. Examples of the black matrix include a black border provided on the periphery of an image display device such as a solid-state imaging device or a liquid crystal display device, a grid-like and / or stripe-like black portion between red, blue, and green pixels, and a dot-like and / or linear black pattern for TFT light shielding.

[0261] The color filter can be produced, for example, by the following method. First, a patterned black matrix is formed on a substrate in the same manner as in the case of the above-mentioned cured film. Then, coating films of red, green, and blue photosensitive coloring compositions are sequentially formed on the substrate on which the black matrix is formed, thereby producing a color filter. The substrate may be a transparent substrate or a reflective substrate. The transparent substrate may be, for example, a glass substrate. The reflective substrate may be, for example, a substrate using an aluminum electrode or a metal thin film as a reflective surface.

[0262] <Image display device> The cured film of the present invention can be used in an image display device. The type of image display device in which the cured film is used is not particularly limited, but examples thereof include a type including a color filter having the above-mentioned black matrix.

[0263] Examples of image display devices include liquid crystal displays and organic EL displays. The configuration used for the image display device is not particularly limited as long as it functions as an image display device. For example, the configuration described in "Next Generation Liquid Crystal Display Technology" (by Tatsuo Uchida, published by Kogyo Chosakai Co., Ltd. in 1994) can be mentioned. The definition of image display devices and details of each image display device are described, for example, in "Electronic Display Devices" (written by Sasaki Akio, published by Kogyo Chosakai Co., Ltd. in 1990) and "Display Devices" (written by Ibuki Nobuaki, published by Sangyo Tosho Co., Ltd. in 1989).

[0264] <Solid-state imaging element> The cured film of the present invention can be used in solid-state imaging devices. The solid-state imaging device may be configured in any manner, including, but not limited to, a substrate having multiple photodiodes and transfer electrodes made of polysilicon or the like that constitute the light-receiving area of a solid-state imaging device (e.g., CCD image sensor, CMOS image sensor), a light-shielding film formed on the photodiodes and transfer electrodes with only the light-receiving portions of the photodiodes exposed, a device protective film made of silicon nitride or the like formed on the light-shielding film to cover the entire light-shielding film and the light-receiving portions of the photodiodes, and a filter on the device protective film. Furthermore, the device protective film may have a light-focusing means (e.g., a microlens, etc.; the same applies hereinafter) below the filter (closer to the substrate) on the device protective film, or a light-focusing means on the filter. The filter may also have a structure in which the cured film forming each color pixel is embedded in spaces partitioned by partition walls, for example, in a grid pattern. In this case, the partition walls preferably have a low refractive index relative to the color pixels. An imaging device including the solid-state imaging element of the present invention can be used for various purposes, such as digital cameras, electronic devices with imaging functions (such as mobile phones and smartphones), vehicle-mounted cameras, surveillance cameras, and infrared sensors.

[0265] The cured film of the present invention can also be used as a colored spacer. For example, when a spacer is used in a TFT-type LCD, light incident on the TFT may cause the TFT to malfunction as a switching element, and the colored spacer is used to prevent this. The colored spacer can be formed in the same manner as the black matrix described above, except that a mask for the colored spacer is used.

[0266] The cured film of the present invention can also be used in applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes). Although not particularly limited, the cured film can be suitably used for optical filters and optical films used in micro LEDs and micro OLEDs, as well as for members that impart light-blocking and anti-reflection properties. Examples of micro LEDs and micro OLEDs include those described in JP-A-2015-500562 and JP-A-2014-533890.

[0267] The cured film of the present invention can also be used in applications such as quantum dot displays. Although not particularly limited, it can be suitably used for optical filters and optical films used in quantum dot displays, as well as for members that impart light-blocking properties and anti-reflection properties. [Example]

[0268] The present invention will be described in more detail below with reference to examples. However, the present invention is not limited to these examples. Note that "parts" means "parts by mass" and "%" means "% by mass." In the present invention, the nonvolatile content or nonvolatile content concentration refers to the mass remaining after leaving the sample to stand in an oven at 230°C for 30 minutes.

[0269] Before describing the examples, each measurement method will be explained.

[0270] The weight average molecular weight (Mw), number average molecular weight (Mn), acid value (mgKOH / g), and amine value (mgKOH / g) of the resin are as follows.

[0271] (average molecular weight of resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was an HLC-8220GPC (Tosoh Corporation). Two separation columns were connected in series, with both columns packed with TSK-GEL SUPER HZM-N. Measurements were performed at an oven temperature of 40°C, a tetrahydrofuran (THF) solution as the eluent, and a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1 wt% of the above eluent, and 20 microliters was injected. The molecular weight is expressed in terms of polystyrene.

[0272] (resin acid value) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of resin solution, and the mixture was stirred to dissolve uniformly. The solution was titrated using an automatic titrator ("COM-555" manufactured by Hiranuma Sangyo Co., Ltd.) with a 0.1 mol / L KOH aqueous solution as the titrant to measure the acid value (mg KOH / g). The acid value per unit of nonvolatile content of the resin was calculated from the acid value of the resin solution and the concentration of nonvolatile content of the resin solution.

[0273] (Amine value of resin) The amine value of the resin is the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 and converted into nonvolatile content.

[0274] <Manufacture of organic pigments> (finely divided blue organic pigment) 100 parts of CI Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyocolor Co., Ltd.), 800 parts of ground sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded for 12 hours at 70°C. This mixture was poured into 3,000 parts of warm water, and stirred in a high-speed mixer for about 1 hour while heated to about 70°C to form a slurry. The sodium chloride and diethylene glycol were removed by repeated filtration and washing with water, and the slurry was then dried overnight at 80°C and pulverized to obtain a finely divided blue organic pigment.

[0275] (finely divided yellow organic pigment) 100 parts of CI Pigment Yellow 139 (Novoperm Yellow P-M3R manufactured by Clariant), 800 parts of pulverized sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded for 12 hours at 70°C. This mixture was added to 3,000 parts of warm water, and stirred for about 1 hour with a high-speed mixer while heated to about 70°C to form a slurry. The sodium chloride and diethylene glycol were removed by repeated filtration and washing with water, and the slurry was then dried overnight at 80°C and pulverized to obtain a finely divided yellow organic pigment.

[0276] (Finely divided purple organic pigment) 100 parts of CI Pigment Violet 23 ("LIONOGEN VIOLET FG-6140" manufactured by Toyocolor Co., Ltd.), 800 parts of pulverized sodium chloride, and 100 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Manufacturing Co., Ltd.) and kneaded for 12 hours at 70°C. This mixture was added to 3,000 parts of warm water, and while heated to about 70°C, the mixture was stirred in a high-speed mixer for about 1 hour to form a slurry. The slurry was filtered and washed with water repeatedly to remove the sodium chloride and diethylene glycol, and then dried overnight at 80°C and pulverized to obtain a finely divided purple organic pigment.

[0277] <Production of Dispersion Resin (B)> (Dispersion resin (B1-1) solution having acidic groups) A reaction vessel equipped with a gas inlet tube, thermostat, condenser, and stirrer was charged with 10 parts methacrylic acid, 100 parts methyl methacrylate, 70 parts i-butyl methacrylate, 20 parts benzyl methacrylate, and 50 parts PGMAc, and the atmosphere was purged with nitrogen gas. The reaction vessel was heated to 50°C with stirring, and 12 parts 3-mercapto-1,2-propanediol was added. The temperature was raised to 90°C, and a solution of 0.1 parts 2,2'-azobisisobutyronitrile in 90 parts propylene glycol monomethyl ether acetate (PGMAc) was added and the reaction was continued for 7 hours. Measurement of the nonvolatile content confirmed that 95% reaction had occurred. 19 parts pyromellitic anhydride, 50 parts PGMAc, 50 parts cyclohexanone, and 0.4 parts 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added, and the reaction was continued for 7 hours at 100°C. The reaction was terminated after confirming that 98% or more of the acid anhydride had been half-esterified by measuring the acid value, and the solution was diluted with PGMAc to a non-volatile content of 30% by measuring the non-volatile content, yielding a dispersion resin (B1-1) solution having acidic groups with an acid value of 70 mg KOH / g and a weight-average molecular weight of 8,500.

[0278] (Dispersion resin (B1-1-2) solution having acidic groups) A reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst. The atmosphere was purged with nitrogen gas, and the reaction was carried out at 120 °C for 5 hours (Step 1). Measurement of the acid value confirmed that 95% or more of the acid anhydride had been half-esterified. Next, 160 parts (based on nonvolatile content) of the compound obtained in Step 1, 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, and the reaction vessel was heated to 80 °C. 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the reaction was carried out for 12 hours (Step 2). It was confirmed by measuring the nonvolatile content that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 parts of hydroquinone were added, and IR showed a 2270 cm peak due to the isocyanate group. -1 The reaction was continued until the disappearance of the peak was confirmed (third step). After the disappearance of the peak was confirmed, the reaction solution was cooled and the nonvolatile content was adjusted with PGMAc to obtain a dispersion resin (B1-1-2) solution having acidic groups with a nonvolatile content of 30%. The acid value of the obtained dispersion resin (B1-1-2) having acidic groups was 68 mg KOH / g, the unsaturated double bond equivalent was 1,593, and the weight average molecular weight was 13,000.

[0279] (Other dispersion resin (B2-1) solution) A reactor equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst. The mixture was stirred at 50 °C for 1 hour under a nitrogen stream, and the system was then purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 100 parts of PGMAc were charged. The temperature was raised to 110 °C under a nitrogen stream to initiate polymerization of the first block (B block). After 4 hours of polymerization, a sample was taken of the polymerization solution and the nonvolatile content was measured. Based on the nonvolatile content, it was confirmed that the polymerization conversion was 98% or higher. Next, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethyl benzyl dimethyl ammonium chloride were added to the reactor. The reaction was continued at 110 °C under a nitrogen atmosphere with stirring. Two hours after addition, the polymerization solution was sampled and the nonvolatile content was measured. Based on the nonvolatile content, it was confirmed that the polymerization conversion rate of the second block (A block) was 98% or higher. The reaction solution was then cooled to room temperature to terminate the polymerization. GPC analysis revealed that the polymer had a mass-average molecular weight of 20,000, a molecular weight distribution (Mw / Mn) of 1.4, and a reaction conversion rate of 98.5%. In this way, a basic dispersion resin (B2-1) with an amine value of 169.8 mg KOH / g per nonvolatile content was obtained. After cooling to room temperature, approximately 2 g was sampled and dried by heating at 180 °C for 20 minutes. The nonvolatile content was measured, and PGMAc was added to obtain a solution of a basic dispersion resin (B2-1) with a nonvolatile content of 30% by mass.

[0280] <Production of polymerizable compound (C)> (Polymerizable compound (C1-1) solution having a urethane bond) A five-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube was charged with 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine, and the temperature was raised to 70°C. A mixture of 64 parts of hexamethylene diisocyanate and 64 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was reacted at a temperature of 50 to 70°C for 8 hours, and the IR was measured at 2180 cm -1 The disappearance of the isocyanate absorption was confirmed. PGMAc was added so that the nonvolatile content was 50 mass %, and an aliphatic urethane acrylate solution having 10 polymerizable unsaturated groups was obtained.

[0281] (Polymerizable compound (C1-2) solution having a urethane bond) A five-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube was charged with 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine, and the temperature was raised to 70°C. A mixture of 84 parts of isophorone diisocyanate and 84 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was reacted at a temperature of 50 to 70°C for 8 hours, and the IR reading was 2180 cm. -1 The disappearance of the isocyanate absorption was confirmed. The nonvolatile content was adjusted to 50 mass %, and an alicyclic urethane acrylate solution having 10 polymerizable unsaturated groups was obtained.

[0282] (Polymerizable compound (C1-3) solution having a urethane bond) A five-neck flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube was charged with 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine, and the temperature was raised to 70°C. A mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropwise addition, the mixture was reacted at a temperature of 50 to 70°C for 8 hours, and the IR reading was 2180 cm. -1The disappearance of the isocyanate absorption was confirmed. Next, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged and reacted at a temperature of 50 to 60°C for 6 hours. The nonvolatile content was adjusted to 50% by mass, and an aromatic urethane acrylate solution having an average number of polymerizable unsaturated groups of 9 was obtained.

[0283] <Production of binder resin (E)> (Binder resin (E1-1) solution) A separable four-neck flask equipped with a thermometer, condenser, nitrogen gas inlet, dropping tube, and stirrer was charged with 100 parts of cyclohexanone and heated to 80°C. The atmosphere inside the reaction vessel was replaced with nitrogen, and then a mixture of 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate (Toagosei Co., Ltd., "Aronix M110"), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. The reaction was continued for another 3 hours after the addition was completed. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried at 180°C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized resin solution to achieve a nonvolatile content of 40% to prepare a binder resin (E1-1). The weight average molecular weight (Mw) was 26,000.

[0284] (Binder resin (E1-2) solution) A separable four-necked flask was fitted with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer. 100 parts of cyclohexanone was charged into the reaction vessel, which was then heated to 80°C and purged with nitrogen. Then, a mixture of 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide-modified acrylate (Toagosei Co., Ltd., Aronix M110), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 1.33 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the addition was complete, the reaction was continued for another 3 hours to obtain a resin solution. Next, the nitrogen gas flow was stopped and the resulting resin solution was stirred with dry air for 1 hour. After cooling to room temperature, a mixture of 6.5 parts of 2-methacryloyloxyethyl isocyanate (Karens MOI, Showa Denko K.K.), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70°C over 3 hours. After the addition was completed, the reaction was continued for another hour. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried at 180°C for 20 minutes to measure the nonvolatile content. Cyclohexanone was added to the previously synthesized resin solution to achieve a nonvolatile content of 40%, preparing a binder resin (E1-2). The weight-average molecular weight (Mw) was 18,000.

[0285] (Binder resin (E1-3) solution) A separable four-neck flask equipped with a thermometer, condenser, nitrogen gas inlet tube, dropping tube, and stirrer was charged with 200 parts of cyclohexanone, heated to 80 ° C, and the atmosphere in the flask was replaced with nitrogen. A mixture of 18 parts of paracumylphenol 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 over 2 hours. After the dropwise addition, the mixture was further reacted at 100 ° C for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile in 20 parts of cyclohexanone was added, and the reaction was continued at 100 ° C for another 1 hour. Next, the vessel was purged with air, and 9.3 parts of acrylic acid (equimolar amount to the glycidyl group), 0.5 parts of tris(dimethylamino)phenol, and 0.1 parts of hydroquinone were added to the vessel. The reaction was continued at 120°C for 6 hours, and terminated when the nonvolatile acid value reached 0.5, yielding an acrylic resin solution. Next, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and the reaction was continued at 120°C for 3.5 hours. After cooling to room temperature, approximately 2 g of the resin solution was sampled and dried at 180°C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized resin solution to achieve a nonvolatile content of 40% by weight, preparing a binder resin (E1-3). The weight-average molecular weight (Mw) was 19,000.

[0286] <Preparation of Dispersion> (Dispersion 1) The following raw materials were mixed and stirred until uniform, then dispersed in an Eiger mill (Eiger Japan, "Mini Model M-250 MKII") using zirconia beads with a diameter of 0.5 mm for 3 hours, and then filtered through a filter with a pore size of 1.0 μm to produce Dispersion 1. The organic solvent (Q-1) was PGMAc. Mitsubishi Chemical #850: 20.0 parts Dispersion resin (B1-1) solution having acidic groups: 26.7 parts Pigment derivative (F-1): 1.3 parts Organic solvent (P-1): 52.0 parts

[0287] Mitsubishi Chemical #850 has an average primary particle diameter of 17 nm and a specific surface area of 220 m 2 / g of carbon black.

[0288] Dye derivative (F-1): The following structure [ka]

[0289] (Dispersion 2~4) Dispersions 2 to 4 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts shown in Table 2 were changed.

[0290] [Table 2]

[0291] Dye derivative (F-2) in Table 2: the following structure [ka]

[0292] <Production of Photosensitive Coloring Composition> [Example 1] (Photosensitive coloring composition 1) The following raw materials were mixed and stirred, and then filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition 1. Dispersion 1: 19.0 parts Polymerizable compound (C1-1) solution having a urethane bond: 6.0 parts Polymerizable compounds having a 9,9-bisarylfluorene structure (C2-1) :3.1 copies Other polymerizable compounds (C3-3): 3.0 parts Compound (D1-1) represented by general formula (1): 0.5 parts Oxime photopolymerization initiator (D2-4): 0.5 parts Binder resin (E): 20.0 parts Sensitizer (G): 0.25 parts Polymerization inhibitor (J): 0.01 parts Leveling agent (M): 1.0 part Organic solvent (P): 46.64 parts

[0293] [Examples 2 to 29, Comparative Examples 1 to 3] (Photosensitive coloring composition 2-32) Photosensitive coloring compositions 2 to 32 were prepared in the same manner as in Example 1, except that the photosensitive coloring composition 1 in Example 1 was changed to the raw materials and amounts shown in Tables 3-1 to 3-4.

[0294] [Table 3-1]

[0295] [Table 3-2]

[0296] [Table 3-3]

[0297] [Table 3-4]

[0298] The raw materials listed in Tables 3-1 to 3-4 are as follows:

[0299] [Polymerizable compound (C)] (Polymerizable compound (C2) having a 9,9-bisarylfluorene structure) C2-1: OGSOL EA-0200 (Osaka Gas Chemicals, glass transition temperature 211°C) C2-2: OGSOL EA-0300 (Osaka Gas Chemicals, glass transition temperature 17°C) C2-3: OGSOL GA-5060P (Osaka Gas Chemicals, glass transition temperature 228°C) C2-4: OGSOL GA-2800 (Osaka Gas Chemicals, glass transition temperature 7°C)

[0300] (Other polymerizable compounds (C3)) C3-1: Aronix M-521 (manufactured by Toagosei) C3-2: KAYARAD DPCA-30 (Nippon Kayaku Co., Ltd.) C3-3: KAYARAD DPHA (Nippon Kayaku Co., Ltd.)

[0301] [Photopolymerization initiator (D)] (Compound (D1) represented by general formula (1)) D1-1: Compound of the above chemical formula (10) D1-2: Compound of the above chemical formula (11) D1-3: Compound of the above chemical formula (12)

[0302] (Oxime-based photopolymerization initiator (D2)) D2-1: Compound of the above chemical formula (13) D2-2: Compound of the above chemical formula (17) D2-3: Compound of the above chemical formula (19) D2-4: Compound of the above chemical formula (20)

[0303] (Other photopolymerization initiators (D3)) D3-1: Omnirad 907 (manufactured by IGM Resins)

[0304] [Binder resin (E)] The binder resin (E1-1) to (E1-3) solutions were mixed in equal amounts to prepare a binder resin (E).

[0305] [Sensitizer (G)] G-1: Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.) G-2:CHEMARK DEABP (manufactured by Chemark Chemical) The above (G-1) and (G-2) were mixed in equal amounts to form a sensitizer (G).

[0306] [Polymerization inhibitor (J)] J-1: 4-methylcatechol J-2: Methylhydroquinone J-3: t-butylhydroquinone The above (J-1) to (J-3) were mixed in equal amounts to prepare a polymerization inhibitor (J).

[0307] [Leveling agent (M)] M-1: BYK-330 (BYK-Chemie) M-2: Megafac F-551 (DIC) One part each of (M-1) and (M-2) was mixed and dissolved in 98 parts of PGMAc to prepare a mixed solution, which was used as a leveling agent (M).

[0308] [Organic solvent (P)] P-1: 30 parts of propylene glycol monomethyl ether acetate P-2: 30 parts cyclohexanone P-3: 10 parts of ethyl 3-ethoxypropionate P-4: Propylene glycol monomethyl ether 10 parts P-5: Cyclohexanol acetate 10 parts P-6: Dipropylene glycol methyl ether acetate 10 parts The above (P-1) to (P-6) were mixed in the above-mentioned parts by mass to prepare the organic solvent (P).

[0309] <Evaluation of Photosensitive Coloring Composition> The obtained photosensitive coloring compositions 1 to 32 (Examples 1 to 29, Comparative Examples 1 to 3) were evaluated for optical density, reflectance, pattern shape, and surface wrinkles by the following methods. The evaluation results are shown in Table 4.

[0310] [Optical density (OD value) evaluation] The obtained photosensitive coloring composition was applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness so that the film thickness after drying would be 2.0 μm. After drying on a hot plate at 70°C for 1 minute, the coating was heated to 30 mW / cm using an ultra-high pressure mercury lamp. 2 , 50 mJ / cm 2The entire surface was exposed to light. The substrate was then spray-developed using organic alkaline developer NMD-3 (Tokyo Ohka Kogyo Co., Ltd.) at 23°C, washed with ion-exchanged water, air-dried, and heated (post-baked) in a clean oven at 230°C for 30 minutes to obtain a cured film. The optical density (OD value) of the obtained cured film was measured using a Macbeth densitometer (GretagMacbeth D200-II). The evaluation criteria are as follows, with a value of 2 or higher being practical. 3: OD value is 2.0 or more 2: OD value is 1.8 or more and less than 2.0 1:OD value is less than 1.8

[0311] [Reflectance evaluation] The cured film prepared by optical density measurement was measured for reflectance (SCI value and SCE value) of color matching function Y using a colorimeter CM-2002 (measurement conditions: C light source, viewing angle 2°) manufactured by Konica Minolta, Inc. The evaluation criteria are as follows, with a value of 3 or higher being practical. The SCI value is an abbreviation for Specular Component Include, which is the total reflectance value, and the SCE value is an abbreviation for Specular Component Exclude, which is the total reflectance value excluding the specular reflected light component. 5: SCI value less than 3.0 and SCE value less than 0.15 4: SCI value is 3.0 or more but less than 3.5, and SCE value is 0.15 or more but less than 0.2 3: SCI value is 3.5 or more and less than 4.0, and SCE value is 0.2 or more and less than 0.25 2: SCI value is 4.0 or more but less than 4.5, and SCE value is 0.25 or more but less than 0.3 1: SCI value is 4.5 or more and SCE value is 0.3 or more

[0312] [Pattern shape evaluation (1): Adhesion] The obtained photosensitive coloring composition was applied by spin coating to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness so that the film thickness after drying would be 2.0 μm, and then dried on a hot plate at 70° C. for 1 minute. Then, after cooling the substrate to room temperature, a high-pressure mercury lamp was used to illuminate the substrate through a photomask with a stripe pattern at 5 μm intervals at an illumination intensity of 30 mW / cm. 2 , 50 mJ / cm 2 The substrate was then spray-developed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23°C, washed with ion-exchanged water, air-dried, and heated in a clean oven at 230°C for 30 minutes to obtain a substrate for adhesion evaluation. The spray development was carried out for the shortest time possible to form a pattern without leaving any residual development for the coating of each photosensitive coloring composition, and this was defined as the appropriate development time. The patterns of 5, 10, 15, 20, and 25 μm widths on the substrates for evaluating pattern formability prepared by the above method were observed under an optical microscope to confirm the minimum line width of the remaining pattern. The evaluation criteria are as follows, with a score of 3 or higher being considered practical. 5: Fine lines of 10 μm or less remain. 4: Fine lines of 15 μm or more remain. 3: Fine lines of 20 μm or more remain. 2: 25 μm fine lines remain. 1: No fine lines remain.

[0313] [Pattern shape evaluation (2): Linearity] The substrate prepared in the pattern shape evaluation (1) was evaluated by measuring the maximum and minimum line widths of the stripe pattern at 10 locations using a Nikon ECLIPSE LV100POL Model optical microscope and calculating the average. The evaluation criteria are as follows, with a score of 3 or higher being practical. 5: The difference between the maximum and minimum line widths is less than 0.5 μm 4: The difference between the maximum and minimum line widths is 0.5 μm or more and less than 1.0 μm 3: The difference between the maximum and minimum line widths is 1.0 μm or more and less than 1.5 μm 2: The difference between the maximum and minimum line widths is 1.5 μm or more and less than 2.0 μm 1: The difference between the maximum and minimum line widths is 2.0 μm or more

[0314] [Surface wrinkle evaluation] The pattern surface of the substrate prepared in the pattern shape evaluation (1) was observed using an optical microscope (Olympus Optical Co., Ltd. "BX-51", magnification: 200 times). The evaluation criteria are as follows, with 3 or more being practical. 5: No wrinkles are observed on the surface of the pattern. 4: Very slight wrinkles are observed on the pattern surface. 3: Slight wrinkles are observed on the surface of the pattern. 2: Wrinkles are observed on the surface of the pattern. 1: Severe wrinkles are observed on the surface of the pattern.

[0315] [Table 4]

Claims

1. A photosensitive coloring composition comprising a black colorant (A), a dispersion resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), the polymerizable compound (C) contains 20 to 80 mass% of a polymerizable compound (C1) having a urethane bond, based on 100 mass% of the polymerizable compound (C), and the molecular weight of the polymerizable compound (C1) having a urethane bond is 500 to 5,000; The photosensitive coloring composition, wherein the photopolymerization initiator (D) comprises a compound (D1) represented by the following general formula (1) and an oxime-based photopolymerization initiator (D2): General formula (1) 【Chemical 1】 (In general formula (1), R １ , R ２ R each independently represents a hydrogen atom or an alkyl group having 1 to 8 carbon atoms. ３ represents a hydrogen atom or a monovalent substituent.

2. 2. The photosensitive coloring composition according to claim 1, wherein the polymerizable compound (C) includes a polymerizable compound (C2) having a 9,9-bisarylfluorene structure.

3. The photosensitive coloring composition according to claim 1 or 2, wherein the dispersing resin (B) comprises a dispersing resin (B1) having an acidic group.

4. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the black colorant (A) comprises carbon black.

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 light-shielding filter comprising the cured film according to claim 5 .

7. A color filter comprising the cured film according to claim 5 .

8. An image display device comprising the cured film according to claim 5 .

9. A solid-state imaging device comprising the cured film according to claim 5 .

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