Photosensitive coloring composition, cured film using the same, light-shielding filter, color filter, image display device, solid-state imaging device, infrared sensor

Abstract

To provide a photosensitive coloring composition which causes less wrinkles during curing and is excellent in developability, pattern formability and light-shielding properties.SOLUTION: The photosensitive coloring composition contains a black colorant (A), a dispersion resin (B) having an acid group, a polymerizable compound (C), a photopolymerization initiator (D), and silica particles (E). The polymerizable compound (C) contains at least one selected from the group consisting of an alicyclic urethane (meth)acrylate (C1) and an aromatic urethane (meth)acrylate (C2).SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to a photosensitive coloring composition, a cured film using the same, a light-shielding filter, a color filter, an image display device, a solid-state imaging device, and an infrared sensor. [Background technology]

[0002] 2. Description of the Related Art Color filters used in image display devices such as liquid crystal and organic electroluminescence devices are provided with 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 units of smartphones, tablet devices, etc. are equipped with light-shielding filters to prevent noise generation and improve image quality.

[0003] Compositions containing black coloring materials such as carbon black and titanium black are known as compositions for forming light-shielding filters. For example, Patent Document 1 discloses a composition for forming a light-shielding film, which is capable of forming a coating film disposed around the periphery of the effective pixel region of a solid-state imaging device and is characterized by containing a black colorant having an average particle diameter of 40 nm or less and a resin component. Furthermore, Patent Document 2 discloses a photosensitive composition for forming partition walls of 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 having 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, although the cured films formed using the compositions described in Patent Documents 1 and 2 have excellent light-blocking properties, they have problems with wrinkles during curing, developability, and pattern formability.

[0006] An object of the present invention is to provide a photosensitive coloring composition that generates little wrinkles when cured, has excellent developability and pattern formability, and has high light-blocking properties. [Means for solving the problem]

[0007] The present invention provides a photosensitive coloring composition comprising a black colorant (A), a dispersion resin having an acid group (B), a polymerizable compound (C), a photopolymerization initiator (D), and silica particles (E), The present invention relates to a photosensitive coloring composition, wherein the polymerizable compound (C) comprises at least one selected from the group consisting of an alicyclic urethane (meth)acrylate (C1) and an aromatic urethane (meth)acrylate (C2).

[0008] The present invention also relates to the above photosensitive coloring composition, wherein the polymerizable compound (C) further contains a polymerizable compound (C3) other than (C1) and (C2).

[0009] The present invention also relates to a method for producing a cycloaliphatic urethane (meth)acrylate (C1) and an aromatic urethane ( The photosensitive coloring composition according to the present invention, wherein the ratio of the total mass of the meth)acrylate (C2) to the mass of the polymerizable compound (C3) other than (C1) and (C2) is 80:20 to 20:80.

[0010] The present invention also relates to the above photosensitive resin composition, wherein the polymerizable compound (C) is an alicyclic urethane (meth)acrylate (C1-a) having an acid group or an aromatic urethane (meth)acrylate (C2-a) having an acid group.

[0011] The present invention also relates to the above photosensitive coloring composition, wherein the black colorant (A) contains carbon black.

[0012] The present invention also relates to the above photosensitive coloring composition, wherein the black colorant (A) contains at least two or more organic pigments selected from a red organic pigment, a yellow organic pigment, a blue organic pigment, and a purple organic pigment.

[0013] The present invention also relates to the above photosensitive coloring composition, which further contains a near-infrared absorber (H).

[0014] The present invention also relates to a cured film obtained by curing the above-mentioned photosensitive coloring composition.

[0015] The present invention also relates to a light-shielding filter having the above-mentioned cured film.

[0016] The present invention also relates to a color filter having the above cured film.

[0017] The present invention also relates to an image display device having the above cured film.

[0018] The present invention also relates to a solid-state imaging device having the above cured film.

[0019] The present invention also relates to an infrared sensor having the above cured film. [Effects of the Invention]

[0020] According to the present invention, it is possible to provide a photosensitive coloring composition that generates little wrinkles during curing, has excellent developability and pattern formability, and has high light-blocking properties. The present invention also provides a cured film, a light-blocking filter, a color filter, an image display device, a solid-state imaging device, and an infrared sensor. [Brief explanation of the drawings]

[0021] [Figure 1] FIG. 1 is a schematic cross-sectional view of an image display device provided with the cured film of the present invention. [Figure 2]FIG. 2 is a schematic cross-sectional view of a solid-state imaging device provided with the cured film of the present invention. [Figure 3] FIG. 3 shows a schematic cross-sectional view of an infrared sensor provided with the cured film of the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0022] 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.

[0023] 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. "CI" stands for The Society Color Index (CI). of Dyers and Colourists). The polymerizable unsaturated group is an ethylenically unsaturated double bond.

[0024] <Photosensitive coloring composition> The present invention provides a photosensitive coloring composition comprising a black colorant (A), a dispersion resin having an acid group (B), a polymerizable compound (C), a photopolymerization initiator (D), and silica particles (E), The photosensitive coloring composition is one in which the polymerizable compound (C) contains at least one selected from the group consisting of alicyclic urethane (meth)acrylates (C1) and aromatic urethane (meth)acrylates (C2).

[0025] The mechanism by which the photosensitive coloring composition having the above-mentioned structure can solve the problems of the present invention is not clear, but the present inventors speculate as follows.

[0026] Photosensitive coloring compositions containing black colorants such as carbon black have been widely used because they can achieve high light-shielding properties over a wide wavelength range. However, for example, when pattern-exposing a photosensitive coloring composition with light in the ultraviolet range such as g-line, h-line, or i-line, the light does not reach the inside of the photosensitive coloring composition layer, which causes problems such as poor adhesion such as chipping or peeling of the cured film during alkaline development, and wrinkles on the surface due to differences in curing shrinkage between the inside and the surface, resulting in a decrease in optical density. However, the silica particles (E) have high transparency, so they form a path for light to pass through the composition layer, which is thought to improve the curing property. Furthermore, at least one selected from the group consisting of alicyclic urethane (meth)acrylates (C1) and aromatic urethane (meth)acrylates (C2) is used. It is believed that the inclusion of the urethane bond portion having a highly rigid alicyclic or aromatic ring structure suppresses shrinkage during curing and reduces the occurrence of wrinkles. The dispersion resin (B) having an acid group is highly soluble in an alkaline developer, and development is completed in a short time, which is thought to prevent chipping and peeling of the cured film. It is presumed that by combining these, a photosensitive coloring composition was obtained that has less wrinkles during curing, is excellent in developability and pattern formability, and has high light-blocking properties.

[0027] [Black colorant (A)] The photosensitive coloring composition of the present invention contains a black colorant (A).

[0028] The black colorant (A) is not particularly limited as long as it exhibits black color, and may be either a pigment or a dye, but is preferably a pigment from the viewpoints of light resistance, heat resistance, and solvent resistance.

[0029] The pigment is not particularly limited, and known inorganic pigments and / or organic pigments can be used.

[0030] (inorganic pigments) Inorganic pigments that can be used for the black colorant (A) 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.

[0031] Examples of carbon black include lamp black, acetylene black, thermal black, channel black, furnace black, etc. Of these, furnace black is preferred.

[0032] 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.

[0033] 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. Of these, the nitrogen BET method is preferred.

[0034] Commercially available carbon black products include, for example, #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, 600 manufactured by Mitsubishi Chemical Corporation, and BLACK PEARLS 460, 800, 880, 900, 1000, 460 manufactured by CABOT. Examples include 840, 1300, 1400, L, REGAL 330, 400, 600, etc.

[0035] (organic pigments) Examples of organic pigments that can be used for the black colorant (A) include perylene compounds such as CI Pigment Black 21, 30, 31, 32, 33, and 34; bisbenzofuranone compounds described in JP-A Nos. 2010-534726, 2012-515233, and 2012-515234; and azomethine compounds described in JP-A Nos. 1-170601 and 2-34664.

[0036] Alternatively, at least two organic pigments selected from a red organic pigment, a yellow organic pigment, a blue organic pigment, and a purple organic pigment may be used as the black colorant (A). In this case, examples of the combination that produces a black color 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 yellow organic pigment, a blue organic pigment, and a purple organic pigment. (5) Contains a red organic pigment, a yellow organic pigment, a blue organic pigment, and a purple organic pigment.

[0037] A specific example of the above embodiment (1) is an embodiment containing at least one selected from CI Pigment Yellow 139, 185, 231, and 233 as a yellow organic pigment, and CI Pigment Violet 23 as a purple organic pigment. A specific example of the above embodiment (2) is an embodiment containing at least one red organic pigment selected from CI Pigment Red 177, 254, 291, 295, and 296, at least one yellow organic pigment selected from CI Pigment Yellow 139, 185, 231, and 233, and CI Pigment Violet 23 as a purple organic pigment. A specific example of the above embodiment (3) is an embodiment containing at least one red organic pigment selected from CI Pigment Red 177, 254, 291, 295, and 296, at least one yellow organic pigment selected from CI Pigment Yellow 139, 185, 231, and 233, and at least one blue organic pigment selected from CI Pigment Blue 15:3, 15:4, and 15:6. A specific example of the above embodiment (4) is CI Pigment Yellow as a yellow organic pigment. 139, 185, 231, 233 as an organic blue pigment, at least one selected from CI Pigment Blue 15:3, 15:4, 15:6 as an organic violet pigment, and CI Pigment Violet 23 as an organic purple pigment. A specific example of the above embodiment (5) is an embodiment containing at least one red organic pigment selected from CI Pigment Red 177, 254, 291, 295, and 296, at least one yellow organic pigment selected from CI Pigment Yellow 139, 185, 231, and 233, at least one blue organic pigment selected from CI Pigment Blue 15:3, 15:4, and 15:6, and at least one violet organic pigment selected from CI Pigment Violet 23.

[0038] Among the above embodiments (1) to (5), the above embodiment (4) is preferred from the viewpoint of light-blocking properties.

[0039] Among the above-mentioned embodiments (4), it is more preferable to contain CI Pigment Yellow 139 as the yellow organic pigment, CI Pigment Blue 15:6 as the blue organic pigment, and CI Pigment Violet 23 as the violet organic pigment.

[0040] Table 1 shows the preferred mass ratios (mass %) of each organic pigment in each embodiment.

[0041] [Table 1]

[0042] (Other colorants) The photosensitive coloring composition of the present invention may contain other colorants in addition to the black colorant (A).

[0043] Other colorants are not particularly limited, and known organic pigments, inorganic pigments, and dyes can be used.

[0044] Examples of organic pigments include compounds classified as pigments in the Color Index. Specifically, 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, 5 7, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 1 51,166,168,169,170,172,173,174,175,176,178,179,181,184,185,187,188,190,193,194,200,202,206,207,208,209,210,214,216,220,221,224,230,231,232,233,235 ,236,237,238,239,242,243,245,247,249,250,251,253,255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276,277,278,279,2 red organic pigments such as those described in Japanese Patent Application Laid-Open No. 2014-134712 and Japanese Patent Application Laid-Open No. 6368844; Orange organic pigments such as CI Pigment Orange 36, 38, 43, 62, 64, 71, and 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-A-2012-226110, ... 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, etc. 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, etc. 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.

[0045] Examples of inorganic pigments include titanium oxide, barium sulfate, zinc oxide, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III)), cadmium red, ultramarine, iron blue, chromium oxide green, and koba. Examples include amber and rut green.

[0046] 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 and laked dyes may also be used.

[0047] 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.

[0048] (Fine pigment particle size) The pigment is preferably used in a finely divided state. The method of finely dividing 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 finely divided 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.

[0049] Salt milling is a process in which a mixture of pigment, water-soluble inorganic salt, and 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 salt mill The pigment is crushed during salt milling, taking advantage of the high hardness of the inorganic salt. By optimizing the conditions for salt milling, it is possible to obtain pigments with extremely fine primary particle diameters and a narrow, sharp particle size distribution.

[0050] 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.

[0051] 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.

[0052] 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.

[0053] [Dispersion resin having acid groups (B)] The photosensitive coloring composition of the present invention contains a dispersing resin (B) having an acid group, which makes it possible to obtain a photosensitive coloring composition having excellent developability and pattern formability.

[0054] Examples of the acidic group include a carboxyl group, a phosphate group, a sulfonic acid group, etc. Among these, from the viewpoint of developability, a carboxyl group and a phosphate group are preferred, and a carboxyl group is more preferred.

[0055] (Dispersion resin (B1) having a carboxyl group) The dispersing resin (B) having an acid group is preferably a dispersing resin (B1) having a carboxyl group. Examples of the dispersing resin (B1) having a carboxyl group include the dispersing resins shown in the following (B1-1) or (B1-2).

[0056] [Dispersion resin having a carboxyl group (B1-1)] The dispersion resin (B1-1) having a carboxyl 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.

[0057] The tetracarboxylic dianhydride is, for example, 1,2,3,4-butanetetracarboxylic acid. Dianhydrides, 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-dioxotetrahydrofural)-3-methyl-3-cyclohexene-1,2-dicarboxylic dianhydride, bicyclo[2.2.2]-octo Aliphatic tetracarboxylic dianhydrides such as 2,3,5,6-tetracarboxylic dianhydride, pyromellitic dianhydride, ethylene glycol ditrimellitic anhydride, propylene glycol ditrimellitic anhydride, butylene glycol ditrimellitic anhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4, 4'-Biphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic acid dianhydride, 3,3',4,4'-tetraphenylsilane tetracarboxylic acid dianhydride, 1,2,3,4-furan tetracarboxylic acid dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfide dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenyl sulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4'-perfluoroisopropyl methyl ether Propylidenediphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic)phenylphosphine oxide dianhydride, p-phenylene-bis(triphenylphthalic) dianhydride, m-phenylene-bis(triphenylphthalic) dianhydride, bis(triphenylphthalic)-4,4'-diphenyl ether dianhydride, 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 and aromatic tetracarboxylic acid dianhydrides such as 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 adsorption to pigments.

[0058] 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.

[0059] Examples of the tricarboxylic acid anhydride include aliphatic tricarboxylic acid anhydrides and aromatic tricarboxylic acid anhydrides.

[0060] 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.

[0061] 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, Examples include 4'-benzophenone tricarboxylic anhydride, 3,4,4'-biphenyl ether tricarboxylic anhydride, 3,4,4'-biphenyl tricarboxylic anhydride, 2,3,2'-biphenyl tricarboxylic anhydride, 3,4,4'-biphenyl methane tricarboxylic anhydride, and 3,4,4'-biphenyl sulfone tricarboxylic anhydride. Among these, aromatic tricarboxylic anhydrides are preferred from the viewpoint of adsorption to pigments.

[0062] 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.

[0063] 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 compounds having two hydroxyl groups and one thiol group in the molecule and at least one hydroxyl group-containing compound selected from the group consisting of vinyl polymers having a hydroxyl group at one end. Examples include 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin or 1-thioglycerol), 2-mercapto-1, Examples thereof include 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.

[0064] Examples of the dispersing resin (B1-1) having a carboxyl group include the following (B1-1-1) and (B1-1-2).

[0065] <<Dispersion resin having a carboxyl group (B1-1-1)>> The vinyl polymer portion of the dispersion resin (B1-1-1) having a carboxyl 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.

[0066] (i-1) [Hydroxyl group-containing monomer] The monomer having a hydroxyl group as a thermal crosslinkable group 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, examples include allyl ether monomers having a hydroxyl group, such as hydroxyalkyl allyl ethers such as 2-hydroxyethyl allyl ether, 2-(or 3-)hydroxypropyl allyl ether, and 2-(or 3- or 4-)hydroxybutyl allyl ether. can be.

[0067] 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.

[0068] (i-2) [Oxetane group-containing monomer] Examples of the monomer having an oxetane group as a thermally crosslinkable group include (vinyloxyalkyl) alkyloxetane, (meth)acryloyloxyalkyloxetane, and [(meth)acryloyloxyalkyl] alkyloxetane. Among these, (3-ethyloxetan-3-yl)methyl methacrylate is preferred. Commercially available products include, for example, ETE RNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate) (manufactured by Ube Industries, Ltd.).

[0069] (i-3) [t-butyl group-containing monomer] Examples of the monomer having a t-butyl group as a thermally crosslinkable functional group include t-butyl methacrylate and t-butyl acrylate.

[0070] (i-4) [Blocked isocyanate group-containing monomer] Monomers having blocked isocyanate groups as thermal crosslinking groups include 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate, 2-[(3,5-di Examples of 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 KK), and the like.

[0071] 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.

[0072] (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.

[0073] (iii) [Other monomers] In the vinyl polymer portion of the dispersing resin (B1-1-1) having a carboxyl group, other monomers than the thermally crosslinkable monomer and the carboxyl group-containing monomer can be used. Other monomers include, for example, methyl (meth)acrylate and ethyl (meth)acrylate. alkyl (meth)acrylates such as 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.

[0074] 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.

[0075] <<Dispersion resin having a carboxyl group (B1-1-2)>> The dispersing resin (B1-1-2) having a carboxyl group has a polymerizable unsaturated group in the vinyl polymer portion.

[0076] The dispersion resin (B1-1-2) having a carboxyl 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 a reaction product of glycidyl methacrylate with a polymer having a hydroxyl group or a carboxyl group, and a reaction product of methacryloyloxyethyl isocyanate with 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 can also be obtained by subjecting a polymer having an acid anhydride group to a ring-opening reaction. For example, the dispersing resin described in JP-A-2011-157416 can be mentioned.

[0077] [Dispersion resin (B1-2) having a carboxyl group] The dispersing resin (B1-2) having a carboxyl group is a dispersing resin represented by the following general formula (1), and specifically, is a dispersing resin described in JP-A-2007-140487.

[0078] General formula (1) (HOOC-) m -R 2 -(-COO-[-R 4 -COO-] n -R 5 ) t (In general formula (3), 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).

[0079] The dispersing resin (B) having an acid group can be used alone or in combination of two or more kinds.

[0080] From the viewpoint of dispersion stability, the content of the dispersing resin (B) having an acid 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).

[0081] The photosensitive coloring composition of the present invention can contain other dispersing resins in addition to the dispersing resin (B) having an acid group.

[0082] (Other dispersion resins) The other dispersing resins are not particularly limited, and known dispersing resins can be used.

[0083] Other commercially available dispersion resins 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 Lubrizol Japan, and E FKA-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 Aji Super PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0084] [Polymerizable compound (C)] The photosensitive coloring composition of the present invention contains, as the polymerizable compound (C), at least one selected from the group consisting of alicyclic urethane (meth)acrylates (C1) and aromatic urethane (meth)acrylates (C2). The urethane bond portion having an alicyclic structure or an aromatic ring structure suppresses cure shrinkage due to the difference in the degree of cure between the surface and the interior of the film during cure, and can more effectively prevent wrinkles from forming on the surface. The polymerizable compound (C) is a monomer, dimer, trimer, or oligomer containing a polymerizable unsaturated group. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.

[0085] (alicyclic urethane (meth)acrylate (C1)) The alicyclic urethane (meth)acrylate (C1) is not particularly limited, and known compounds can be used. Examples include a compound obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate having an alicyclic structure, and a compound obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate having an alicyclic structure, and then reacting the resulting mixture with a (meth)acrylate having a hydroxyl group.

[0086] 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, and dipentaerythritol ethylene oxide-modified penta(meth)acrylate. Examples include 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.

[0087] 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.

[0088] (Aromatic urethane (meth)acrylate (C2)) The aromatic urethane (meth)acrylate (C2) is not particularly limited, and any known aromatic urethane (meth)acrylate 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 (C1) to a polyfunctional isocyanate having an aromatic ring structure.

[0089] Examples of the polyfunctional isocyanate having an aromatic ring structure include 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzyl isocyanate, dialkyldiphenylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-toluene diisocyanate, 2,6-toluene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4,4-diphenylmethane diisocyanate, tolylene diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, and bis(isocyanatemethyl)benzene. Further examples include biuret derivatives, isocyanate nurate derivatives, and trimethylolpropane adducts thereof.

[0090] The number of polymerizable unsaturated groups in the alicyclic urethane (meth)acrylate (C1) and aromatic urethane (meth)acrylate (C2) is preferably 3 to 15, more preferably 5 to 12, from the viewpoints of pattern formability and wrinkle prevention.

[0091] From the viewpoint of inhibiting wrinkles, the photosensitive coloring composition of the present invention preferably contains an aromatic urethane (meth)acrylate (C2).

[0092] From the viewpoint of developability, the photosensitive coloring composition of the present invention is preferably an alicyclic urethane (meth)acrylate (C1-a) having an acid group or an aromatic urethane (meth)acrylate (C2-a) having an acid group. Examples of the acid group include a sulfonic acid group, a carboxyl group, and a phosphate group. Among these, a carboxyl group is preferred.

[0093] (Alicyclic urethane (meth)acrylate (C1-a) having an acid group) The alicyclic urethane (meth)acrylate (C1-a) having an acid group can be synthesized, for example, by first reacting the (meth)acrylate having a hydroxyl group with the polyfunctional isocyanate having an alicyclic structure, and then adding a mercapto compound having a carboxyl group to the reaction product.

[0094] 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.

[0095] (Aromatic urethane (meth)acrylate (C2-a) having an acid group) The aromatic urethane (meth)acrylate (C2-a) having an acid group can be synthesized in the same manner as the alicyclic urethane (meth)acrylate (C1-a) having an acid group.

[0096] (Polymerizable compound (C3) other than (C1) and (C2)) From the viewpoint of pattern formability, the photosensitive coloring composition of the present invention preferably contains a polymerizable compound (C3) other than (C1) and (C2) (hereinafter also referred to as other polymerizable compound (C3)).

[0097] 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, and tricyclodecamethyl. Dimethylmethanol 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 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, those having 5 or more polymerizable unsaturated groups are preferred from the viewpoint of pattern formability.

[0098] 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 Aronik manufactured by Toagosei Co., Ltd. M-303,M-305,M-306,M-309,M-310,M-321,M-325,M-350,M-360,M-313,M-315,M-400,M-402,M -403,M-404,M-405,M-406,M-450,M-452,M-408,M-211B,M-101A,M-5300,M-5400,M-5700,M-510 , M-520, M-521, OGSOL EA-0200, EA-0300, GA-5060P, GA-2800 manufactured by Osaka Gas Chemicals Co., Ltd., Miramer HR6060, 6100, 6200 manufactured by Miwon Specialty Chemical Co., Ltd., Viscoat #2500P manufactured by Osaka Organic Chemicals Co., Ltd., NK Ester ABE-300, A-DOG, A-DCP, A-BPE-4 manufactured by Shin-Nakamura Chemical Co., Ltd., and EBECRY40, 130, 140, 145 manufactured by Daicel-Allnex Co., Ltd.

[0099] From the viewpoint of pattern formability and suppression of wrinkles on the surface, the ratio of the total mass of the alicyclic urethane (meth)acrylate (C1) and the aromatic urethane (meth)acrylate (C2) to the mass of the other polymerizable compound (C3) is preferably 80:20 to 20:80, and more preferably 70:30 to 30:70.

[0100] The content of the polymerizable compound (C) is preferably from 5 to 50 mass %, more preferably from 5 to 30 mass %, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition.

[0101] [Photopolymerization initiator (D)] The photosensitive coloring composition of the present invention contains a photopolymerization initiator (D). By containing the photopolymerization initiator (D), the photosensitive coloring composition can be cured by ultraviolet irradiation to form a cured film.

[0102] Examples of the photopolymerization initiator (D) include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, and 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; Oxime ester compounds such as 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)], or ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime); 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.

[0103] Commercially available acetophenone compounds include "Omnirad 907" (2-methyl-1-[4-(methylthio)phenyl]-2-morpholino) manufactured by IGM Resins. The compounds used were: 2-(dimethylamino)-1-[4-(4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, Omnirad 369E (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone), Omnirad 379EG (2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone); acylphosphine compounds: Omnirad 819 (bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide) and Omnirad TPO (diphenyl-2,4,6-trimethylbenzoylphosphine oxide) manufactured by IGM Resins; and oxime compounds: 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)] (IRGACURE) manufactured by BASF. OXE-01), ethanol, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-, 1-(O-acetyloxime) (IRGACURE OXE-02), IRGACURE OXE-03, IRGACURE OXE-04, N-1919, NCI-730, NCI-831, and NCI-930 manufactured by ADEKA Corporation, and TRONLY TR-PBG-304, TRONLY TR-PBG-305, TRONLY TR-PBG-309, TRONLY TR-PBG-345, and TRONLY TR-PBG-3054 manufactured by Changzhou Strong New Materials Co., Ltd. Further examples include the oxime compounds described in JP 2007-210991 A, JP 2009-179619 A, JP 2010-037223 A, JP 2010-215575 A, JP 2011-020998 A, and International Publication WO 2015 / 036910. Among these, from the viewpoint of pattern formability, oxime compounds are preferred, and compounds represented by the following chemical formula (2) are more preferred.

[0104] Chemical formula (2) [ka]

[0105] The method for producing the compound of chemical formula (2) is not particularly limited, and a known method can be used, for example, the method described in International Publication WO2015 / 036910.

[0106] The photopolymerization initiator (D) can be used alone or in combination of two or more kinds.

[0107] The content of the photopolymerization initiator (D) is preferably from 2 to 50 parts by mass, more preferably from 2 to 30 parts by mass, relative to 100 parts by mass of the black colorant (A) from the viewpoints of photocurability and developability.

[0108] [Silica particles (E)] The photosensitive coloring composition of the present invention contains silica particles (E).

[0109] The silica particles (E) are not particularly limited, and known silica particles can be used.

[0110] Examples of the silica particles (E) include dry silica and wet silica such as colloidal silica. Therefore, colloidal silica is preferred because the particle shape and size can be easily controlled.

[0111] The silica particles (E) are preferably spherical in shape from the viewpoint of the surface smoothness of the cured film.

[0112] From the viewpoint of preventing wrinkles, the average primary particle size of the silica particles (E) is preferably from 1 to 100 nm, more preferably from 5 to 50 nm, and particularly preferably from 10 to 30 nm.

[0113] Commercially available silica particles (E) include, for example, PL-1-IPA, PL-1-TOL, PL-2L-PGME, and PL-2L-MEK manufactured by Fuso Chemical Co., Ltd., YA010C-LDI and YA050C-LHI manufactured by Admatechs Co., Ltd., and MA-ST-M, MA-ST-L, IPA-ST, IPA-ST-L, IPA-ST-UP, EG-ST, NPC-ST-30, PGM-ST, MEK-ST-40, MEK-ST-UP, MIBK-ST, MIBK-ST-L, and CHO- ST-M, EAC-ST, PMA-ST, TOL-ST, DMAC-ST, MEK-AC-2140Y, MEK-AC-4130Y, MEK-AC-5140Z, PGM-AC-2140Z, PEM-AC-4130Y, MIBK-AC -4130Y, MIBK-AC-2140Y, MIBK-SD-L, MEK-EC-2130Y, MEK-EC-6150P, MEK-EC-7150P, EP-F2130Y, EP-F6140P, EP-F7150P, etc.

[0114] From the viewpoint of pattern formability and wrinkle suppression, the content of the silica particles (E) is preferably 5 to 30 mass %, more preferably 10 to 25 mass %, based on 100 mass % of the nonvolatile content of the photosensitive coloring composition.

[0115] [Dye derivative (F)] The photosensitive coloring composition of the present invention may contain a dye derivative (F).

[0116] 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.

[0117] 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.

[0118] The dye derivative (F) can be used alone or in combination of two or more kinds.

[0119] 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).

[0120] [Binder resin (G)] The photosensitive coloring composition of the present invention may contain a binder resin (G), which improves the heat resistance, chemical resistance, and other resistances of the cured film.

[0121] The binder resin (G) is not particularly limited, and known resins can be used.

[0122] The binder resin (G) can be classified into a non-photosensitive binder resin and a photosensitive binder resin. Furthermore, from the viewpoint of developability, the binder resin (G) preferably 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. Among these, a carboxyl group is preferred. The binder resin (G) may also contain a thermosetting group such as an epoxy group or an oxetanyl group.

[0123] (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.

[0124] (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.

[0125] [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. The generated hydroxyl groups are reacted with a polybasic acid anhydride to obtain a photosensitive binder resin.

[0126] 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.

[0127] 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.

[0128] 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.

[0129] 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.

[0130] 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.

[0131] [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.

[0132] 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.

[0133] Examples of the isocyanate group-containing monomer include 2-(meth)acryloylethyl isocyanate, 2-(meth)acryloyloxyethyl isocyanate, and 1,1-bis[methacryloyloxy]ethyl isocyanate.

[0134] The monocarboxyl group-containing monomer and other monomers that can be used are those described above.

[0135] 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.

[0136] The binder resin (G) can be used alone or in combination of two or more kinds.

[0137] From the viewpoint of developability, the weight average molecular weight (Mw) of the binder resin (G) is preferably 2,000 to 40,000, more preferably 3,000 to 300,000, and particularly preferably 4,000 to 20,000. The value of Mw / Mn is preferably 10 or less. An appropriate weight average molecular weight (Mw) improves adhesion to the substrate and alkaline developability.

[0138] The acid value of the binder resin (G) is preferably 50 to 200 mgKOH / g, more preferably 70 to 180 mgKOH / g, and even more preferably 90 to 170 mgKOH / g. A suitable acid value improves adhesion to a substrate and alkaline developability.

[0139] The content of the binder resin (G) 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).

[0140] [Near infrared absorber (H)] When the photosensitive coloring composition of the present invention is used in a solid-state imaging device, it preferably contains a near-infrared absorber (H), which makes it possible to control the transmission of near-infrared rays of a specific wavelength and improves the separation from the near-infrared region. The near-infrared absorber (H) is a compound that absorbs light with a wavelength of 750 to 1,200 nm.

[0141] Examples of the near-infrared absorber (H) include cyanine compounds, phthalocyanine compounds, naphthalocyanine compounds, immonium compounds, pyrrolopyrrole compounds, squarylium compounds, croconium compounds, etc. Among these, cyanine compounds, pyrrolopyrrole compounds, and squarylium compounds are preferred.

[0142] Among the near-infrared absorbers (H), cyanine compounds are disclosed in International Publication Nos. WO2006 / 006573, WO2010 / 073857, JP2013-241598A, JP2016-113501A, and JP2016-113504A; phthalocyanine compounds are disclosed in Japanese Patent Application Laid-Open Nos. H4-23868A, H06-192584A, JP2000-63691A, and WO2014 / 208514; naphthalocyanine compounds are disclosed in Japanese Patent Application Laid-Open Nos. H11-152414A, JP2000-86919A, JP2009-29955A, and WO2018 / 186490; and immonium compounds are disclosed in , JP 2005-336150 A, JP 2007-197492 A, JP 2008-88426 A; pyrrolopyrrole compounds are disclosed in JP 2009-263614 A, JP 2010-90313 A, JP 2011-068731 A; squarylium compounds are disclosed in JP 2011-132361 A , JP 2016-142891 A, WO 2017 / 135359 A, WO 2018 / 225837 A, JP 2019-001987 A, WO 2020 / 054718 A; croconium compounds include compounds described in WO 2019 / 021767 A, etc.

[0143] The near-infrared absorbing agent (H) can be used alone or in combination of two or more kinds.

[0144] The content of the near-infrared absorber (H) is preferably 10 to 200 parts by mass, more preferably 15 to 150 parts by mass, and particularly preferably 20 to 100 parts by mass, relative to 100 parts by mass of the black colorant (A).

[0145] [Sensitizer (I)] The photosensitive coloring composition of the present invention can contain a sensitizer (I).

[0146] Examples of the sensitizer (I) 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, and squarylium derivatives. compounds, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalyloporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler's ketone derivatives, α-acyloxy esters, acyl oxides, methylphenyl Examples include methyl glycyoxylate, 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.

[0147] Among the sensitizers (I), thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred, and specific 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.

[0148] The sensitizer (I) can be used alone or in combination of two or more kinds.

[0149] The content of the sensitizer (I) 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.

[0150] [Thermosetting compound (J)] The photosensitive coloring composition of the present invention can contain a thermosetting compound (J), which reacts in the heating step to increase the crosslink density and improve the heat resistance.

[0151] The thermosetting compound (J) may be a low molecular weight compound or a high molecular weight compound such as a resin. Examples of the thermosetting compound (J) 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.

[0152] (Epoxy compound (J-1)) Examples of the epoxy compound (J-1) 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.) with various aldehydes (formaldehyde, acetaldehyde, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.), polycondensates of phenols with various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinyl Examples of 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. can be done.

[0153] 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.

[0154] From the viewpoint of heat resistance of the cured film, the content of the epoxy compound (J-1) is preferably from 0.5 to 300 parts by mass, and more preferably from 1.0 to 50 parts by mass, per 100 parts by mass of the black colorant (A).

[0155] (Oxetane Compound (J-2)) The oxetane compound (J-2) is a known compound having an oxetane group, and examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or higher functional oxetane compounds.

[0156] Examples of the monofunctional oxetane compound include (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, and 3-ethyl-3- Examples thereof include 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.

[0157] 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.

[0158] 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.

[0159] Examples of commercially available products include OXBP and OXTP manufactured by Ube Industries, Ltd., and OXT-121 and 221 manufactured by Toagosei Co., Ltd.

[0160] 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.

[0161] The content of the oxetane compound (J-2) 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.

[0162] 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.

[0163] 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.

[0164] Among these, Nikarak 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.

[0165] The thermosetting compound (J) can be used alone or in combination of two or more kinds.

[0166] [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 (J). 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 derivatives, bicyclic amidine compounds and their salts (e.g., imidazole, 2-methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, and 1-(2-cyanoethyl)-2-ethyl-4-methylimidazole, etc.), phosphorus compounds (e.g., triphenylphosphine, etc.), 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.).

[0167] The curing agents can be used alone or in combination of two or more.

[0168] 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 (J).

[0169] [Thiol-based chain transfer agent (K)] The photosensitive coloring composition of the present invention can contain a thiol-based chain transfer agent (K). When the thiol-based chain transfer agent (K) is used in combination with the photopolymerization initiator (D), during radical polymerization after light irradiation, a thiyl radical that is not easily inhibited by oxygen is generated, and the photosensitivity of the photosensitive coloring composition is improved.

[0170] The thiol chain transfer agent (K) is preferably a polyfunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol chain transfer agent has four or more SH groups. As the number of functional groups increases, photocuring becomes easier from the surface to the deepest part of the film.

[0171] 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.

[0172] The thiol chain transfer agent (K) can be used alone or in combination of two or more kinds.

[0173] The content of the thiol chain transfer agent (K) is preferably 1 to 10 parts by mass, more preferably 2 to 8 parts by mass, per 100 parts by 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.

[0174] [Polymerization inhibitor (L)] The photosensitive coloring composition of the present invention may contain a polymerization inhibitor (L).

[0175] The polymerization inhibitor (L) is, for example, catechol, resorcinol, 1,4-hydroquinone. alkyl catechol compounds such as 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propylcatechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-t-butylcatechol, 3-t-butylcatechol, 4-t-butylcatechol, and 3,5-di-t-butylcatechol; 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, and 4-n-butyl Examples of suitable phosphine compounds include alkylresorcinol compounds such as resorcinol, 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.

[0176] The content of the polymerization inhibitor (L) is preferably 0.01 to 0.4% by mass in 100% by mass of the nonvolatile content of the photosensitive coloring composition.

[0177] [Ultraviolet absorber (M)] The photosensitive coloring composition of the present invention can contain an ultraviolet absorber (M).

[0178] The ultraviolet absorber (M) 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.

[0179] 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.

[0180] Commercially available products include, for example, TINUVIN P, PS, 234, 32 manufactured by BASF Japan Ltd. 6,329,384-2,900,928,99-2,1130, ADK STAB LA-29, LA-31RG, LA-32, LA-36 manufactured by ADEKA CORPORATION, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Chemical Co., Ltd., and RUVA-93 manufactured by Otsuka Chemical Co., Ltd.

[0181] 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.

[0182] Commercially available products include KEMISORB 102 manufactured by Chemipro Chemicals Co., Ltd. and BASF Japan TINUVIN 400, 405, 460, 477, 479, 1577ED, AD manufactured by the company EKA ADK STAB LA-46, LA-F70, Sun Chemical CYASORB UV-1164 and the like.

[0183] 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.

[0184] Commercially available products include, for example, KEMISORB 10, 11, 11S, and 12 manufactured by Chemipro Chemicals. ,111, Seesorb 101,107 manufactured by Shipro Chemical Co., Ltd., Adeka manufactured by ADEKA Co., Ltd. Examples include Stab 1413 and UV-12 manufactured by Sun Chemical.

[0185] Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butylphenyl salicylate.

[0186] The content of the ultraviolet absorber (M) is preferably 5 to 70% by mass relative to 100% by mass of the total of the photopolymerization initiator (D) and the ultraviolet absorber (M).

[0187] [Antioxidant (N)] The photosensitive coloring composition of the present invention may contain an antioxidant (N). The antioxidant (N) is The photopolymerization initiator (D) and thermosetting compound (J) contained in the photosensitive coloring composition prevent yellowing due to oxidation during the thermal process of heat curing or ITO annealing. In particular, when the concentration of organic pigment (A) in the photosensitive coloring composition is high, the content of polymerizable compound (C) decreases relatively, and if the amount of photopolymerization initiator (D) is increased or a thermosetting compound is added to address this, the cured film is likely to yellow. Therefore, the inclusion of an antioxidant prevents yellowing of the cured film due to oxidation during the heating process.

[0188] Examples of the antioxidant (N) include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In the present invention, the antioxidant is preferably a compound that does not contain a halogen atom.

[0189] Among these, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred.

[0190] 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.

[0191] 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.

[0192] Examples of the hindered amine antioxidant include tetrakis(1,2,2,6,6-pentaerythritol). Methyl-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 methacrylate, 2,2,6,6-tetramethyl-4 -piperidyl methacrylate, polycondensation product 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]], ester of 4-hydroxy-2,2,6,6-tetramethyl-1-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-bis(1,1dimethylethyl)-4-hydroxyphenyl]methyl]butanol Tilmalonate methyl 1,2,2,6,6-pentamethyl-4-pyripridyl sebacate, poly[[6-morpholino-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2,2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid esters, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6-hexamethylenediamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc.

[0193] 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.

[0194] 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.

[0195] 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.

[0196] 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.

[0197] Examples of commercially available products include Adekastab AO-412S and AO-503 manufactured by ADEKA Corporation, and KEMINOXPLS manufactured by Chemipro Chemicals.

[0198] The antioxidant (N) can be used alone or in combination of two or more kinds.

[0199] The content of the antioxidant (N) 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.

[0200] [Leveling agent (O)] The photosensitive coloring composition of the present invention can contain a leveling agent (O). This further improves the wettability to the substrate during application and the drying property. Examples of the leveling agent (O) include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

[0201] Examples of silicone surfactants include linear polymers consisting of siloxane bonds and modified siloxane polymers in which organic groups have been introduced into the side chains or terminals.

[0202] 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.

[0203] Examples of the fluorine-based surfactant include a surfactant or leveling agent having a fluorocarbon chain.

[0204] 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.

[0205] 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.

[0206] 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.

[0207] 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.

[0208] Examples of commercially available products include Acetamine 24, Cortamine 24P, 60W, and 86P Concentrate, manufactured by Kao Corporation.

[0209] 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.

[0210] 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.

[0211] 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.

[0212] Commercially available products include Anhithol 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, and 20N manufactured by Kao Corporation.

[0213] The leveling agent (O) can be used alone or in combination of two or more kinds.

[0214] The content of the leveling agent (O) 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. Within this range, the balance between the coatability and adhesion of the photosensitive coloring composition is further improved.

[0215] [Storage stabilizer (P)] The photosensitive coloring composition of the present invention can contain a storage stabilizer (P). This stabilizes the viscosity of the photosensitive coloring composition over time. Examples of the storage stabilizer (P) 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.

[0216] The content of the storage stabilizer (P) is preferably 0.1 to 10 parts by mass relative to 100 parts by mass of the black colorant (A).

[0217] [Adhesion improver (Q)] The photosensitive coloring composition of the present invention may contain an adhesion improver (Q), which improves the adhesion between the cured film and the substrate and also makes it easier to form narrow patterns by photolithography.

[0218] Examples of the adhesion improver (Q) include silane coupling agents. Examples of the silane coupling agent include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane. (meth)acrylic silanes such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, epoxy silanes such as N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butyl)- silane coupling agents such as aminosilanes such as 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.

[0219] The adhesion improver (Q) can be used alone or in combination of two or more kinds.

[0220] The content of the adhesion improver (Q) 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).

[0221] [Organic solvent (R)] The photosensitive composition of the present invention may contain an organic solvent (R).

[0222] Examples of the organic solvent (R) 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.

[0223] The organic solvent (R) can be used alone or in combination of two or more kinds.

[0224] [Method for producing photosensitive coloring composition] The photosensitive coloring composition of the present invention can be produced by, for example, adding a black colorant (A), a dispersing resin (B) having an acid group, a dye derivative (F), an organic solvent (R), and the like, and dispersing the mixture. The composition can then be produced by blending and mixing a polymerizable compound (C), a photopolymerization initiator (D), silica particles (E), a binder resin (G), and the like. The timing of blending each material is optional. The dispersion process can also be performed multiple times.

[0225] 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.

[0226] 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.

[0227] 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.

[0228] 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.

[0229] <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.

[0230] [Method of manufacturing cured film] The method for producing the cured film is not particularly limited. For example, a photosensitive coloring composition is applied to a substrate. The film can be produced by carrying out the steps of (1) forming a layer of the composition, (2) patternwise exposing the layer to light through a mask, (3) developing the unexposed portions with alkali to form a patternwise cured film, and (4) heat-treating (post-baking) the pattern.

[0231] 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.

[0232] (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.

[0233] (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.

[0234] Examples of the developing method include a dipping method, a spraying method, and a paddle method. The developing temperature is preferably 15 to 40° C. After the alkaline development, it is preferable to wash with pure water. .

[0235] (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.

[0236] [Properties of cured film] The optical density (hereinafter also referred to as OD value) of the cured film obtained by curing the photosensitive coloring composition of the present invention at a film thickness of 2.0 μm is preferably 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.

[0237] The method for measuring the thickness of the cured film is as follows.

[0238] (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 would be 2.0 μm, and after drying on a hot plate at 70° C. for 1 minute, it was irradiated with 250 mJ / cm 2 using an ultra-high pressure mercury lamp. 2 After that, the substrate was exposed to 0.2% by mass of After spray development using an aqueous sodium carbonate solution, the resist was 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 thickness of 2.0 μm includes the tolerance range acceptable in the technical field to which the present invention pertains, specifically, a thickness of 2.0 μm±0.2 μm.

[0239] (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.

[0240] <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.

[0241] <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.

[0242] 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.

[0243] <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.

[0244] An example of the image display device of the present invention will be described. An image display device includes the color filter of the present invention and a light source. Examples of light sources include cold cathode fluorescent lamps (CCFLs) and white LEDs. In the present invention, it is preferable to use white LEDs because they broaden the red reproduction range. Fig. 1 is a schematic cross-sectional view showing an example of the configuration of an image display device including the cured film of the present invention. The image display device 10 shown in Fig. 1 includes a pair of transparent substrates 11 and 21 arranged at a distance from each other, with a liquid crystal LC sealed between them.

[0245] A TFT (thin film transistor) array 12 is formed on the inner surface of the first transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. A polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0246] On the other hand, a color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. Red, green, and blue filter segments that make up the color filter 22 are separated by a black matrix (not shown).

[0247] A transparent protective film (not shown) is formed as needed to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of that, and an alignment layer 24 is provided to cover the transparent electrode layer 23.

[0248] A polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Below the polarizing plate 25, a backlight unit 30 is provided.

[0249] Liquid crystal displays (LC) are available in various types: TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), and OCB (Optically Compensated). The first transparent substrate 1 is oriented in accordance with a driving mode such as birefringence. A TFT (thin film transistor) array 12 is formed on the inner surface of the transparent substrate 11, and a transparent electrode layer 13 made of, for example, ITO is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. A polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

[0250] On the other hand, a color filter 22 of the present invention is formed on the inner surface of the second transparent substrate 21. Red, green, and blue filter segments that make up the color filter 22 are separated by a black matrix (not shown).

[0251] A transparent protective film (not shown) is formed as needed to cover the color filter 22, and a transparent electrode layer 23 made of, for example, ITO is formed on top of that, and an alignment layer 24 is provided to cover the transparent electrode layer 23.

[0252] A polarizing plate 25 is formed on the outer surface of the transparent substrate 21. Below the polarizing plate 25, a backlight unit 30 is provided.

[0253] The white LED light source includes a blue LED with a fluorescent filter formed on the surface, and a blue LED with a fluorescent material contained in the resin package, and has a wavelength (λ3) in the range of 430 nm to 485 nm at which the emission intensity becomes maximum, a wavelength (λ4) in the range of 530 nm to 580 nm at which the emission intensity becomes maximum, and a wavelength (λ5) in the range of 600 nm to 650 nm at which the emission intensity becomes maximum, and the ratio (I4 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less. Therefore, a white LED light source (LED1) having spectral characteristics in which the ratio (I5 / I3) of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 is 0.1 or more and 1.3 or less, or a white LED light source (LED2) having a wavelength (λ1) at which the emission intensity is maximum in the range of 430 nm to 485 nm, a peak wavelength (λ2) of the second emission intensity in the range of 530 nm to 580 nm, and a ratio (I2 / I1) of the emission intensity I1 at wavelength λ1 to the emission intensity I2 at wavelength λ2 is 0.2 or more and 0.7 or less is preferred.

[0254] Specific examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Corporation) and NSSW304D-HG-V1 (manufactured by Nichia Corporation).

[0255] Specific examples of the LED 2 include NSSW440 (manufactured by Nichia Chemical Industries, Ltd.) and NSSW304D (manufactured by Nichia Chemical Industries, Ltd.).

[0256] <Solid-state imaging element> The cured film of the present invention can be used in a solid-state imaging device. The form of the solid-state imaging device used is not particularly limited, but examples include a substrate having a plurality of photodiodes constituting the light-receiving area of the solid-state imaging device (such as a CCD image sensor, a CMOS image sensor, or an organic CMOS image sensor) and a light-receiving element made of polysilicon or the like, and the cured film of the present invention on the side of the light-receiving element formation surface or the opposite side of the formation surface. Figure 2 is a schematic cross-sectional view showing an example of the configuration of a solid-state imaging device provided with the cured film of the present invention.

[0257] As shown in FIG. 2, the solid-state imaging device 200 includes a rectangular solid-state imaging element 201 and a transparent cover glass 203 that is held above the solid-state imaging element 201 and seals the solid-state imaging element 201. Furthermore, a lens layer 211 is provided on the cover glass 203 via a spacer 104. The lens layer 211 is composed of a support 213 and a lens material 212. When stray light enters the peripheral region of the lens layer 211, the light diffusion weakens the light-collecting effect of the lens material 212, resulting in a reduction in the amount of light that reaches the imaging unit 202. Furthermore, noise due to the stray light also occurs. Therefore, the peripheral region of the lens layer 211 is provided with a cured film (light-shielding) 214 of the present invention to shield it from light.

[0258] The solid-state imaging element 201 photoelectrically converts an optical image formed on an imaging section 202, which serves as its light-receiving surface, and outputs the converted image signal. The solid-state imaging element 201 includes a laminated substrate 205 formed by laminating two substrates. The laminated substrate 205 is made up of a rectangular chip substrate 206 and a circuit substrate 207 of the same size, with the circuit substrate 207 laminated on the back surface of the chip substrate 206.

[0259] An imaging unit 202 is provided in the center of the surface of the chip substrate 206. Furthermore, if stray light is incident on the peripheral region of the imaging unit 202, a dark current (noise) is generated from the circuit in this peripheral region, and therefore, this peripheral region is provided with a cured film (light-shielding) 215 of the present invention to shield it from light.

[0260] A plurality of electrode pads 208 are provided on the edge of the surface of the chip substrate 206. The electrode pads 208 are electrically connected to the imaging unit 202 via signal lines (not shown) provided on the surface of the chip substrate 206.

[0261] External connection terminals 209 are provided on the rear surface of the circuit board 207 at positions approximately below the electrode pads 208. Each external connection terminal 209 is connected to each electrode pad 208 via a through electrode 210 that vertically penetrates the laminated substrate 205. Each external connection terminal 209 is also connected via wiring (not shown) to a control circuit that controls the driving of the solid-state imaging element 201, an image processing circuit that performs image processing on an imaging signal output from the solid-state imaging element 201, and the like.

[0262] <Infrared sensor> The cured film of the present invention can be used in an infrared sensor. Fig. 3 is a schematic cross-sectional view showing an example of the configuration of an infrared sensor including the cured film of the present invention. The infrared sensor 300 shown in Fig. 3 includes a solid-state imaging element 310.

[0263] The imaging area provided on the solid-state imaging element 310 is made up of an infrared absorbing filter 311 and a color filter. The filter 312 is configured in combination with the filter 312. The infrared absorbing filter 311 transmits light in the visible light range (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared range (for example, light with a wavelength of 800 to 1300 nm). The color filter 312 is a color filter formed with pixels that transmit and absorb light of specific wavelengths in the visible light range, and for example, a color filter formed with red (R), green (G), and blue (B) pixels is used.

[0264] Between the infrared transmission filter 313 and the solid-state imaging element 310, a resin film 314 that is capable of transmitting light of the wavelength that has passed through the infrared transmission filter 313 is disposed. The infrared transmission filter 313 is a filter that has visible light blocking properties and transmits infrared rays of a specific wavelength, and the cured film of the present invention containing the above-mentioned near-infrared absorber (H) can be used for the infrared transmission filter 313. The infrared transmission filter 113 preferably blocks light with a wavelength of 400 to 830 nm and transmits light with a wavelength of 900 to 1300 nm, for example.

[0265] A microlens 315 is disposed on the incident light side of the color filter 312 and the infrared transmission filter 313. A planarization film 316 is formed so as to cover the microlens 315.

[0266] In the embodiment shown in FIG. 3, the resin film 314 is disposed, but instead of the resin film 314, an infrared transmission filter 313 may be formed.

[0267] The cured film of the present invention can be used as a light-shielding film for the edge and / or side of the surface of the infrared absorbing filter 311, and when used on the inner wall of an infrared sensor, it can prevent internal reflection and / or the incidence of unwanted light into the light-receiving part, thereby improving sensitivity.

[0268] This infrared sensor can simultaneously capture image information, enabling motion sensing that recognizes the movement of an object. Furthermore, this infrared sensor can also acquire distance information, making it possible to capture images that include 3D information. Furthermore, this infrared sensor can also be used as a biometric authentication sensor.

[0269] 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.

[0270] 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.

[0271] 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]

[0272] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, "parts" means "parts by mass" and "%" means "% by mass."

[0273] Before describing the examples, each measurement method will be explained.

[0274] The weight average molecular weight (Mw), number average molecular weight (Mn), and acid value (mgKOH / g) of the resin are as follows:

[0275] (Average molecular weight of binder resin and dispersing resin) The number-average molecular weight (Mn) and weight-average molecular weight (Mw) of the binder resin and dispersing resin were measured using gel permeation chromatography (GPC) equipped with an RI detector. The instrument used was a Tosoh HLC-8220GPC. Two separation columns were connected in series, both 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.

[0276] (Acid value of binder resin and dispersing resin) 80 ml of acetone and 10 ml of water were added to 0.5 to 1 g of binder resin and dispersed resin solution, and the mixture was stirred to dissolve uniformly. The mixture was then 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 then calculated from the acid value of the resin solution and the concentration of nonvolatile content of the resin solution.

[0277] (Amine value of dispersion resin) The amine value of the dispersing resin is the total amine value (mgKOH / g) measured in accordance with the method of ASTM D 2074 and converted into solid content.

[0278] <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 for about 1 hour in a high-speed mixer while heated to about 70°C to form a slurry. The slurry was filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol, and then dried overnight at 80°C to obtain a finely divided blue organic pigment.

[0279] (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 slurry was filtered and washed repeatedly with water to remove the sodium chloride and diethylene glycol, and then dried overnight at 80°C to obtain a finely divided yellow organic pigment.

[0280] (Finely divided purple organic pigment) 100 parts of CI Pigment Violet 23 ("LIONOGEN VIOLET FG-6140" 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 Seisakusho Co., Ltd.) and kneaded at 70°C for 12 hours. This mixture was added to 3,000 parts of hot water and heated to approximately 70°C. The mixture was stirred in a high-speed mixer for about 1 hour to form a slurry, which was then filtered and washed repeatedly with water to remove sodium chloride and diethylene glycol, and then dried at 80°C overnight to obtain a finely divided purple organic pigment.

[0281] <Production of Dispersion Resin (B) Having Acid Groups> (Carboxyl group-containing dispersion resin (B1-1) solution) 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 carboxyl groups with an acid value of 70 mgKOH / g and a weight-average molecular weight of 8,500.

[0282] (Carboxyl group-containing dispersion resin (B2-1-1) solution) 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). Measurement of the nonvolatile content confirmed that 95% of the mixture 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 the reaction was continued until the disappearance of the peak at 2270 cm-1 due to the isocyanate group was confirmed by IR (third step). After confirming the disappearance of the peak, the reaction solution was cooled, and the nonvolatile content was adjusted with PGMAc to obtain a dispersion resin (B2-1-1) solution with acid groups and a nonvolatile content of 30%. The acid value of the resulting dispersion resin (B2-1-1) with carboxyl groups was 68 mg KOH / g, the unsaturated double bond equivalent was 1,593, and the weight-average molecular weight was 13,000.

[0283] <Production of other dispersion resin solutions> (Solution of Dispersion Resin (1) Having Basic Groups) 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 while flowing nitrogen, and the system was purged with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate as an initiator, 5.6 parts of cuprous chloride as a catalyst, and 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, the polymerization solution was sampled 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 methacryloyloxyethyl benzyl dimethyl methacrylate were added to the reactor. Ten parts of ammonium chloride were added, and the reaction was continued by stirring while maintaining the temperature at 110°C under a nitrogen atmosphere. Two hours after addition, a sample of the polymerization solution was taken 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 (1) with an amine value of 169.8 mg KOH / g per nonvolatile content was obtained. After cooling to room temperature, approximately 2 g of the solution was sampled and dried by heating at 180°C for 20 minutes. The nonvolatile content was measured, and PGMAc was added to obtain a dispersion resin (1) solution with basic groups, with a nonvolatile content of 30% by mass.

[0284] <Production of alicyclic urethane (meth)acrylate (C1) and aromatic urethane (meth)acrylate (C2)> (alicyclic urethane acrylate (C1-1) solution) 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 pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine, and the temperature was raised to 70°C. A mixture of 148 parts of isophorone diisocyanate and 100 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 ー1 The disappearance of the isocyanate absorption was confirmed. PGMAc was added so that the nonvolatile content was 50 mass %, and a solution of an alicyclic urethane acrylate (C1-1) having 6 polymerizable unsaturated groups was obtained.

[0285] (Aromatic urethane acrylate (C2-1) solution) 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 pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine, and the temperature was raised to 70°C. A mixture of 107 parts of 1,3-phenylenediisocyanate and 100 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 ー1 The disappearance of the isocyanate absorption was confirmed. PGMAc was added so that the nonvolatile content was 50 mass %, and a solution of aromatic urethane acrylate (C2-1) having 6 polymerizable unsaturated groups was obtained.

[0286] (Aromatic urethane acrylate (C2-2) solution) 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 66 parts of toluene diisocyanate (a mixture of 2,4 and 2,6 isomers) and 100 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. ー1 The disappearance of the isocyanate absorption was confirmed. PGMAc was added so that the nonvolatile content was 50 mass %, and a solution of aromatic urethane acrylate (C2-2) having 10 polymerizable unsaturated groups was obtained.

[0287] (Alicyclic urethane acrylate (C1-a-1) solution having acid groups) 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 pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine, and the temperature was raised to 70°C. A mixture of 148 parts of isophorone diisocyanate and 100 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 ー1 The disappearance of the isocyanate absorption was confirmed. Next, 61 parts of mercaptoacetic acid and 0.4 parts of 4-methoxyphenol were charged and reacted for 6 hours at a temperature of 50 to 60°C. PGMAc was added so that the nonvolatile content became 50% by mass, and a solution of aromatic urethane acrylate (C2-a-1) having an average of 5 polymerizable unsaturated groups and having acid groups was obtained.

[0288] (Aromatic urethane acrylate (C2-a-1) solution having acid groups) A five-neck flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube was charged with 400 parts of pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 parts of N,N-dimethylbenzylamine, and the temperature was raised to 70°C. A mixture of 116 parts of toluene diisocyanate (a mixture of 2,4 and 2,6 isomers) and 100 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 concentration was measured by IR at 2180 cm. ー1 The disappearance of the isocyanate absorption was confirmed. Next, 66 parts of mercaptoacetic acid and 0.4 parts of 4-methoxyphenol were charged and reacted for 6 hours at a temperature of 50 to 60°C. PGMAc was added so that the nonvolatile content was 50% by mass, and a solution of aromatic urethane acrylate (C2-a-1) having an average of 5 polymerizable unsaturated groups and having acid groups was obtained.

[0289] (Aromatic urethane acrylate (C2-a-2) solution having acid groups) 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 61 parts of 1,3-phenylenediisocyanate and 61 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. ー1 The disappearance of the isocyanate absorption was confirmed. Next, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged and reacted for 6 hours at a temperature of 50 to 60°C. PGMAc was added so that the nonvolatile content became 50% by mass, and a solution of aromatic urethane acrylate (C2-a-2) having an average of 9 polymerizable unsaturated groups and having acid groups was obtained.

[0290] <Production of Other Polymerizable Compounds (C3)> (Aliphatic urethane acrylate (C3-1) solution) 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 ー1 The disappearance of the isocyanate absorption was confirmed. PGMAc was added so that the nonvolatile content was 50 mass %, and a solution of an aliphatic urethane acrylate (C3-1) having 10 polymerizable unsaturated groups was obtained.

[0291] <Production of binder resin (G)> (Binder resin (G-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. After the addition was completed, the reaction was continued for another 3 hours to obtain an acrylic resin solution. 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 (G-1). The weight average molecular weight (Mw) was 26,000.

[0292] (Binder resin (G-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. After that, 20 parts of methacrylic acid and ethylenediaminetetraacetic acid were added through the dropping tube. 20 parts of oxide-modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2'-azobis( ... A mixture of 1.33 parts isobutyronitrile was added dropwise over 2 hours. After completion of the addition, the reaction continued for an additional 3 hours to obtain a copolymer resin solution. The nitrogen gas supply was stopped and dry air was injected into the resulting copolymer solution for 1 hour while stirring. After cooling to room temperature, a mixture of 6.5 parts 2-methacryloyloxyethyl isocyanate (Karens MOI, Showa Denko K.K.), 0.08 parts dibutyltin laurate, and 26 parts cyclohexanone was added dropwise at 70°C over 3 hours. After completion of the addition, the reaction continued for another 1 hour to obtain an acrylic resin solution. 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%, to prepare a binder resin (G-2). The weight-average molecular weight (Mw) was 18,000.

[0293] (Binder resin (G-3) solution) A separable four-neck flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer was charged with 200 parts of cyclohexanone, and the temperature was raised to 80°C. The atmosphere in the flask was replaced with nitrogen, and then 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 2,2'-azobisisobutyronite were added through the dropping tube. A mixture of 2.0 parts of glycidyl nitrile was added dropwise over 2 hours. After the dropwise addition, the reaction was continued for another 3 hours at 100°C, followed by the addition of a solution of 1.0 parts of azobisisobutyronitrile in 20 parts of cyclohexanone, and the reaction was continued for another hour at 100°C. Next, the atmosphere in the vessel was purged with air, and 9.3 parts of acrylic acid (100% of glycidyl groups), 0.5 parts of trisdimethylaminophenol, and 0.1 parts of hydroquinone were added to the vessel. The reaction was continued for 6 hours at 120°C, and the reaction was 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 for 3.5 hours at 120°C, yielding an acrylic resin solution. 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 resin solution synthesized earlier to obtain a nonvolatile content of 40% by mass, and a binder resin (G-3) solution was prepared. The weight-average molecular weight (Mw) was 19,000.

[0294] (Binder resin (G-4) solution) A separable flask equipped with a condenser was prepared as a reaction vessel. On the other hand, a monomer dropping vessel containing 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, 120 parts of methyl methacrylate, 4 parts of t-butylperoxy 2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation), and 40 parts of PGMAc was prepared with thorough stirring. A chain transfer agent dropping vessel containing 8 parts of n-dodecanethiol and 32 parts of PGMAc was prepared with thorough stirring. 200 parts of PGMAc was charged into the reactor, and the atmosphere was replaced with nitrogen. The reactor temperature was then raised to 90°C by heating in an oil bath with stirring. After the reactor temperature stabilized at 90°C, dropwise addition was initiated from the monomer dropper and chain transfer agent dropper. The dropwise addition took 135 minutes, maintaining the temperature at 90°C. Sixty minutes after the dropwise addition was completed, the temperature was raised to 110°C. After maintaining the temperature at 110°C for three hours, a gas inlet tube was attached to the separable flask, and bubbling with a 5 / 95 (volume ratio) oxygen / nitrogen mixed gas began. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were charged into the reactor, and the reaction was continued at 110°C for 12 hours. After that, 150 parts of PGMAc was added and the mixture was cooled 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 then added to the resin solution synthesized earlier to obtain a binder resin (G-4) solution with a weight-average molecular weight of 18,000 and an acid value of 2 mgKOH / g per nonvolatile content.

[0295] (Binder resin (G-5) solution) A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube was charged with 150 parts of PGMAc, and the atmosphere in the flask was changed from air to nitrogen. After that, the temperature was raised to 100°C, and a solution prepared by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 70.5 parts (0.40 mol) of benzyl methacrylate, 71.1 parts (0.50 mol) of glycidyl methacrylate, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 164 parts of PGMAc was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued for a further 5 hours at 100°C. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 parts of methacrylic acid (0.5 mol, 100 mol% relative to the glycidyl groups of the glycidyl methacrylate used in this reaction), 0.9 parts of tris(dimethylaminomethyl)phenol, and 0.145 parts of hydroquinone were added to the flask. The reaction was continued at 110 °C for 6 hours, and the reaction was terminated when the nonvolatile acid value reached 1 mg KOH / g. Next, 60.9 parts (0.40 mol) of tetrahydrophthalic anhydride and 0.8 parts of triethylamine were added, and the reaction was continued at 120 °C for 3.5 hours to obtain a photosensitive transparent resin solution with an acid value of 80 mg KOH / g. After cooling to room temperature, approximately 2 parts of the photosensitive transparent resin solution was sampled and dried at 180 °C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized photosensitive transparent resin solution so that the nonvolatile content reached 40% by mass, to prepare a binder resin (G-5) solution. The mass average molecular weight (Mw) was 12,000.

[0296] (Binder resin (G-6) solution) A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen inlet tube was charged with 150 parts of PGMAc, and the atmosphere in the flask was changed from air to nitrogen. After that, the temperature was raised to 100°C, and a solution prepared by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 70.5 parts (0.40 mol) of benzyl methacrylate, 43.0 parts (0.5 mol) of methacrylic acid, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 136 parts of PGMAc was added dropwise from the dropping funnel to the flask over 2 hours, and stirring was continued for a further 5 hours at 100°C. Next, the atmosphere in the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate [0.25 mol (50 mol% relative to the carboxyl groups of the methacrylic acid used in this reaction)], 0.9 parts of tris(dimethylaminomethyl)phenol, and 0.145 parts of hydroquinone were added to the flask. The reaction was continued at 110 °C for 6 hours, resulting in a photosensitive transparent resin solution with an acid value of 79 mg KOH / g. After cooling to room temperature, approximately 2 parts of the photosensitive transparent resin solution was sampled and heated to 180 °C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized photosensitive transparent resin solution to achieve a nonvolatile content of 40% by weight, producing a binder resin (G-6) solution. The weight-average molecular weight (Mw) was 13,000.

[0297] <Production of Near-Infrared Absorbent (H)> (Near infrared absorber (H-1)) 400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 3 hours. Water produced during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the dark brown solid obtained by distilling the toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added. The mixture was refluxed for 3 hours under a nitrogen gas atmosphere. The mixture was then heated and stirred for 3 hours under a nitrogen gas atmosphere. The water produced during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the dark brown solid obtained by distilling the toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The obtained brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol, and 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added. The mixture was heated and stirred in an atmosphere under reflux for 8 hours, and the water produced during the reaction was removed from the reaction system by azeotropic distillation. After the reaction was completed, the solvent was distilled off, and the resulting reaction mixture was stirred while adding 200 parts of hexane. The resulting black-brown precipitate was filtered off, washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain a near-infrared absorber (H-1) represented by the following chemical formula (3). 50 parts of the obtained near-infrared absorber (H-1), 500 parts of sodium chloride, and 60 parts of diethylene glycol were charged into a stainless steel gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60°C for 12 hours. Next, the kneaded mixture was poured into hot water and stirred for 1 hour while heating to approximately 80°C to form a slurry. The mixture was then filtered and washed with water to remove the sodium chloride and diethylene glycol, and then dried overnight at 80°C and pulverized to obtain a finely divided near-infrared absorber (H-1).

[0298] Chemical formula (3) [ka]

[0299] <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 (R-1) was PGMAc. Carbon black (Mitsubishi Chemical #850): 20.0 parts Dispersion resin (B1-1) solution having an acid group: 26.7 parts Pigment derivative (F-1): 1.3 parts Organic solvent (R-1): 52.0 parts

[0300] 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.

[0301] Dye derivative (F-1): The following structure [ka]

[0302] (Dispersion 2~5) Dispersions 2 to 5 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts shown in Table 2 were changed.

[0303] [Table 2]

[0304] Dye derivative (F-2) in Table 2: the following structure [ka]

[0305] <Production of Photosensitive Coloring Composition> [Example 1] (Photosensitive coloring composition 1) The following raw materials were mixed and stirred, and filtered through a filter with a pore size of 1.0 μm to obtain photosensitive coloring composition 1. obtained. Dispersion 1: 19.0 parts Alicyclic urethane acrylate (C1-1) solution: 12.0 parts Photopolymerization initiator (D-1): 0.4 parts Silica particles (E): 7.7 parts Binder resin (G) solution: 20.0 parts Polymerization inhibitor (L): 0.01 parts Antioxidant (N): 0.1 parts Leveling agent (O): 1.0 part Storage stabilizer (P): 0.2 parts Organic solvent (R): 39.62 parts

[0306] [Examples 2 to 26, Comparative Examples 1 to 5] (Photosensitive coloring composition 2-31) Photosensitive coloring compositions 2 to 31 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 3-3.

[0307] [Table 3-1]

[0308] [Table 3-2]

[0309] [Table 3-3]

[0310] The raw materials listed in Tables 3-1 to 3-3 are as follows:

[0311] [Polymerizable compound (C)] (Other polymerizable compounds (C3)) C3-2: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate, non-volatile content 100%) C3-3: Aronix M-521 (manufactured by Toagosei Co., Ltd., 5 polymerizable unsaturated groups, acid group, non-volatile content 100%) C3-4: OGSOL EA-0200 (Osaka Gas Chemicals, number of polymerizable unsaturated groups: 2, non-volatile content: 100%)

[0312] [Photopolymerization initiator (D)] D-1: Compound represented by the above chemical formula (2) D-2: Irgacure 907 (BASF)

[0313] [Silica particles (E)] PMA-ST (Nissan Chemical Co., Ltd., primary particle size 12 nm, non-volatile content 30%)

[0314] [Binder resin (G) solution] The binder resin (G-1) to (G-6) solutions were mixed in equal amounts to prepare a binder resin (G) solution.

[0315] [Sensitizer (I)] I-1: Kayacure DETX-S (Nippon Kayaku Co., Ltd.) I-2:CHEMARK DEABP (manufactured by Chemark Chemical) The above (I-1) and (I-2) were mixed in equal amounts to prepare sensitizer (I).

[0316] [Thiol-based chain transfer agent (K)] Pentaerythritol tetrakis(3-mercaptopropionate)

[0317] [Polymerization inhibitor (L)] L-1: 4-methylcatechol L-2: Methylhydroquinone L-3: t-butylhydroquinone The above (L-1) to (L-3) were mixed in equal amounts to prepare a polymerization inhibitor (L).

[0318] [Antioxidant (N)] N-1: Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] N-2: Dioctadecyl 3,3'-thiodipropanoate N-3: Tris[2,4-di-(t)-butylphenyl]phosphine N-4: Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate N-5: p-Octylphenyl salicylate The above (N-1) to (N-5) were mixed in equal amounts to prepare an antioxidant (N).

[0319] [Leveling agent (O)] O-1: BYK-330 (BYK-Chemie) O-2: Megafac F-551 (DIC) One part each of (O-1) and (O-2) was mixed and dissolved in 98 parts of PGMAc. The mixed solution was used as a leveling agent (O).

[0320] [Storage stabilizer (P)] P-1: 2,6-bis(1,1-dimethylethyl)-4-methylphenol P-2: Triphenylphosphine The above (P-1) and (P-2) were mixed in equal amounts to prepare a storage stabilizer (P).

[0321] [Organic solvent (R)] R-1: 30 parts of propylene glycol monomethyl ether acetate R-2: 30 parts cyclohexanone R-3: 10 parts of ethyl 3-ethoxypropionate R-4: Propylene glycol monomethyl ether 10 parts R-5: Cyclohexanol acetate 10 parts R-6: Dipropylene glycol methyl ether acetate 10 parts The above (R-1) to (R-6) were mixed in the above-mentioned parts by mass to prepare an organic solvent (R).

[0322] <Evaluation of Photosensitive Coloring Composition> The obtained photosensitive coloring compositions 1 to 31 (Examples 1 to 26, Comparative Examples 1 to 5) were evaluated for optical density, developability, pattern formability, and surface wrinkles by the following methods. The evaluation results are shown in Table 4.

[0323] [Table 4]

[0324] [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, and the coating was dried on a hot plate at 70°C for 1 minute. After that, the coating was heated at 250 mJ / cm using an ultra-high pressure mercury lamp. 2 After that, the substrate was exposed to light in an organic alcohol solution at 23°C. After spray development using potassium developer NMD-3 (Tokyo Ohka Kogyo Co., Ltd.), the film was washed with ion-exchanged water, air-dried, and 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 were as follows: 2 or more is practically feasible. 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

[0325] [Developability evaluation] The obtained photosensitive coloring composition was applied to a glass substrate (Corning Eagle 2000) measuring 100 mm in length, 100 mm in width, and 0.7 mm in thickness using a spin coater so that the dry film thickness was 2.0 μm, and then dried on a hot plate at 70° C. for 1 minute. Then, an ultra-high pressure mercury lamp was used to apply the coating with an illuminance of 30 mW / cm. 2 , 250 mJ / cm 2 The substrate was exposed to ultraviolet light through a photomask with a 100 μm-wide stripe pattern. After cooling to room temperature, the substrate was spray-developed using organic alkaline developer NMD-3 (Tokyo Ohka Kogyo Co., Ltd.) at 23°C for two development times (40 seconds and 70 seconds), washed with ion-exchanged water, and air-dried. The resulting substrate was post-baked in a clean oven at 230°C for 30 minutes, forming a striped pattern on the substrate. The pattern was observed under an optical microscope to evaluate the presence or absence of development residues and chipping in unexposed areas. The results are as follows, with a score of 2 or higher being practical. 3: After a development time of 70 seconds, there was no development residue in the unexposed areas and no pattern defects. 2: At a development time of 70 seconds, development residue or pattern defects occurred in the unexposed areas. 1: At a development time of 40 seconds, development residue or pattern defects occurred in the unexposed areas.

[0326] [Pattern Formability 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 apply the photosensitive coloring composition to the substrate through a photomask with a 100 μm wide (200 μm pitch) and 10 μm wide (20 μm pitch) stripe pattern at an illuminance of 30 mW / cm. 2 , 250 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. Of the patterns on the substrate for evaluating adhesion, fine line patterns with widths of 6 to 25 μm were observed under an optical microscope to confirm the minimum line width of the remaining fine line patterns. 5: Fine lines of 10 μm or less remain. 4: Fine lines of 15 μm or less remain. 3: Fine lines of 20 μm or less remain. 2: Fine lines of 25 μm or less remain. 1: No fine lines remain.

[0327] [Pattern formation evaluation (2): Linearity] The substrate prepared in the pattern formability evaluation (1) was evaluated by measuring the maximum and minimum line widths of 10 stripe patterns using a Nikon ECLIPSE LV100POL Model optical microscope and calculating the average. The evaluation criteria are as follows, with 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

[0328] [Surface wrinkle evaluation] The pattern surface of the substrate prepared for adhesion evaluation was observed using an optical microscope (Olympus Optical Co., Ltd. "BX-51", magnification: 200x). The evaluation criteria are as follows, with 3 or higher 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. [Explanation of symbols]

[0329] 10 Image display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color Filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing Plate 30 Backlight unit 31 White LED light source LC liquid crystal

[0330] 200 Solid-state imaging device 201 Solid-state imaging device 202 Imaging unit 203 Cover Glass 204 Spacer 205 Laminated Board 206 Chip Substrate 207 Circuit Board 208 Electrode Pads 209 External connection terminal 210 Through electrode 211 Lens Layer 212 Lens material 213 Support 214 Cured film (light shielding) 215 Cured film (light shielding)

[0331] 300 Infrared Sensor 310 Solid-state imaging device 311 Infrared absorbing filter 312 Color Filter 313 Infrared absorption and transmission filter 314 Resin Film 315 Microlens 316 Flat film

Claims

1. A photosensitive coloring composition comprising a black colorant (A), a dispersion resin having an acid group (B), a polymerizable compound (C), a photopolymerization initiator (D), and silica particles (E), A photosensitive coloring composition, wherein the polymerizable compound (C) contains an aromatic urethane (meth)acrylate (C2).

2. The photosensitive coloring composition described in claim 1, wherein the polymerizable compound (C) may contain an alicyclic urethane (meth)acrylate (C1), and the polymerizable compound (C) further contains a polymerizable compound (C3) other than (C1) and (C2).

3. The photosensitive coloring composition according to claim 2, wherein the ratio of the total mass of the alicyclic urethane (meth)acrylate (C1) and the aromatic urethane (meth)acrylate (C2) to the mass of the polymerizable compound (C3) other than (C1) and (C2) is 80:20 to 20:

80.

4. A photosensitive resin composition described in any one of claims 1 to 3, wherein the aromatic urethane (meth)acrylate (C2) is an aromatic urethane (meth)acrylate (C2-a) having an acid group.

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

6. The black colorant (A) contains at least two or more organic pigments selected from a red organic pigment, a yellow organic pigment, a blue organic pigment, and a purple organic pigment. The photosensitive coloring composition according to any one of claims 1 to 4.

7. The photosensitive coloring composition according to any one of claims 1 to 6, further comprising a near-infrared absorber (H).

8. A cured film obtained by curing the photosensitive coloring composition according to any one of claims 1 to 7.

9. A light-shielding filter comprising the cured film according to claim 8.

10. A color filter comprising the cured film according to claim 8.

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

12. A solid-state imaging device comprising the cured film according to claim 8 .

13. An infrared sensor comprising the cured film according to claim 8.

Images