JP2023159488A - Photosensitive coloring compositions and applications thereof - Google Patents

Abstract

To provide photosensitive coloring compositions with low wrinkle generation during curing, excellent developability and pattern formability, and high light-shielding properties.SOLUTION: A photosensitive coloring composition comprises a black colorant (A), a dispersion resin (B), a polymerizable compound (C), and a photoinitiator (D), where the photoinitiator (D) includes an oxime-based photoinitiator (D1) represented by the general formula in the figure.SELECTED DRAWING: Figure 1

Description

The present invention relates to a photosensitive coloring composition containing a black colorant and uses thereof.

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

A composition containing a black coloring agent such as carbon black or titanium black is used as a composition for forming a light blocking filter. For example, Patent Document 1 describes a composition for forming a light-shielding film containing carbon black or titanium black with an average particle diameter of 40 nm or less and a resin component, which can form a coating film disposed around the periphery of an effective pixel area of a solid-state image sensor. is disclosed. Further, Patent Document 2 describes an optical element containing a photocurable alkali-soluble resin having an ethylenically unsaturated double bond, a photopolymerization initiator, a black pigment, and hollow fine particles with an average primary particle diameter of 20 to 100 nm. A photosensitive composition for forming barrier ribs is disclosed.

Japanese Patent Application Publication No. 2006-156801 Japanese Patent Application Publication No. 2011-48195

However, although the cured films formed using the compositions described in Patent Documents 1 and 2 have excellent light-shielding properties, they have problems with wrinkles, developability, and pattern formability during curing.

An object of the present invention is to provide a photosensitive coloring composition that causes less wrinkles during curing, has excellent developability and pattern-forming properties, and has high light-shielding properties.

The present invention is a photosensitive coloring composition comprising a black colorant (A), a dispersion resin (B), a polymerizable compound (C), and a photopolymerization initiator (D),
A photosensitive coloring composition in which the photopolymerization initiator (D) contains an oxime photopolymerization initiator (D1) represented by the following general formula (1).
General formula (1)


(In the general formula (1), R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or Represents 2 to 20 heterocyclic groups.
R ₂ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₃ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₄ represents any monovalent substituent. n represents an integer from 0 to 3. )

According to the above-mentioned present invention, it is possible to provide a photosensitive coloring composition that causes less wrinkles during curing, has excellent developability and pattern formation properties, and has high light-shielding properties. Further, the present invention can provide a cured film, a light shielding filter, a color filter, an image display device, a solid-state image sensor, and an infrared sensor.

FIG. 1 shows a schematic cross-sectional view of an image display device equipped with the cured film of the present invention. FIG. 2 shows a schematic cross-sectional view of a solid-state imaging device provided with the cured film of the present invention. FIG. 3 shows a schematic cross-sectional view of an infrared sensor equipped with the cured film of the present invention.

Below, the form for carrying out the photosensitive coloring composition of this invention is demonstrated in detail. Note that the present invention is not limited to the following embodiments, and can be modified and implemented within the scope that can solve the problem.

In the present invention, "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" are respectively used unless otherwise specified. , means "acryloyl and/or methacryloyl", "acrylic and/or methacrylic", "acrylic acid and/or methacrylic acid", "acrylate and/or methacrylate", or "acrylamide and/or methacrylamide" . Further, "C.I." means Color Index (C.I.; published by The Society of Dyers and Colorists). The polymerizable unsaturated group is an ethylenically unsaturated double bond.
In addition, regarding the molecular weight of the compound in the present invention, for low-molecular compounds whose molecular weight can be specified, the molecular weight is the value calculated by calculation or the molecular weight measured by ESI-MS (electrospray ionization mass spectrometry), and the molecular weight distribution is The weight average molecular weight of the compound in terms of polystyrene is measured by gel permeation chromatography using tetrahydrofuran as a solvent.

<Photosensitive coloring composition>
One embodiment of the present invention relates to a photosensitive coloring composition. The photosensitive coloring composition of the present invention is a photosensitive coloring composition containing a black colorant (A), a dispersion resin (B), a polymerizable compound (C), and a photopolymerization initiator (D),
The photopolymerization initiator (D) is a photosensitive coloring composition containing an oxime photopolymerization initiator (D1) represented by the following general formula (1). The photosensitive coloring composition can form a film having light blocking properties. The film can be patterned by, for example, photolithography. The pattern is used, for example, as a black matrix in a color filter, an infrared transmission filter in a solid-state image sensor, a frame part in a liquid crystal display, and the like. Although the film contains the black colorant (A) that is difficult for light to pass through, due to the action of the oxime photopolymerization initiator (D1), a practically sufficient degree of curing can be obtained from the surface of the film to the deep part of the film. .
General formula (1)


(In general formula (1), R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or Represents 2 to 20 heterocyclic groups.
R ₂ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₃ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₄ represents any monovalent substituent. n represents an integer from 0 to 3. )

Components that are or can be included in the photosensitive composition of one embodiment will be described in detail below.

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

Examples of the black colorant (A) include cases in which a single type of colorant produces black color, or cases in which two or more types of colorants are mixed to appear black or almost black. Examples of the black colorant (A) include pigments and dyes, but pigments are preferable from the viewpoints of light resistance, heat resistance, and solvent resistance.

Examples of pigments include inorganic pigments and organic pigments.

(Inorganic pigment)
Inorganic pigments include, for example, metal elements of group 4 such as titanium and zirconium, metal elements of group 5 such as vanadium and niobium, cobalt, chromium, copper, manganese, ruthenium, iron, nickel, tin, and silver. Metal oxides, metal nitrides, metal oxynitrides, carbon black, etc. containing one or more metal elements selected from the group consisting of: Two or more of these inorganic pigments may be used in combination, and in order to improve light-shielding properties, organic pigments and dyes described below may be used in combination. Among these, carbon black is preferred because it is inexpensive and can form a film with high light-shielding properties in a small amount.

Examples of carbon black include lamp black, acetylene black, thermal black, channel black, and furnace black. Among these, furnace black is preferred.

The average primary particle diameter of carbon black is preferably 10 to 30 nm, more preferably 10 to 20 nm. When the particle size is appropriate, it is easy to achieve both light-shielding properties and curability. Note that the average primary particle diameter is the average of approximately 20 arbitrary particles displayed in an enlarged 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. and ask. In addition, when a particle has a length in the major axis direction and a minor axis direction, the length in the major axis direction is used.

The specific surface area of carbon black is preferably from 100 to 500 m ² /g, more preferably from 150 to 400 m ² /g, from the viewpoint of light-shielding properties. A known method can be used to measure the specific surface area. For example, it can be determined by adsorbing iodine, nitrogen (BET method, STSA method), cetyltrimethylammonium bromide, etc. on the surface of carbon black. Among these, the nitrogen BET method is preferred.

Commercially available carbon blacks include, for example, #30, 30L, 32, 40, 44, 45, 45L, 47, 52, 650, 850, 900, 950, 960, 980, 1000, 1000N, 2300 manufactured by Mitsubishi Chemical Corporation. ,2350,2600,2650,3230,3400,4000,MCF88,MA7,8,11,77,100,230,600,BLACKPEARLS460,800,880,900,1000,4 made by CABOT
Examples include 840, 1300, 1400, L, REGAL 330, 400, 600, and the like.

(organic pigment)
Organic pigments include, for example, C.I. I. Perylene compounds such as Pigment Black 21, 30, 31, 32, 33, and 34, bisbenzofuranone compounds described in Japanese Translated Patent Publication No. 2010-534726, Japanese Translated Patent Publication No. 2012-515233, and Japanese Transparent Publication No. 2012-515234, Examples include black organic pigments such as azomethine compounds described in JP-A-1-170601 and JP-A-2-34664.

Alternatively, the black colorant (A) may be made using at least two or more organic pigments selected from the group consisting of a red organic pigment, a yellow organic pigment, a green organic pigment, a blue organic pigment, and a violet organic pigment. At this time, examples of combinations that exhibit black color include the following embodiments.
(1) Contains a yellow organic pigment and a purple organic pigment.
(2) Contains a red organic pigment, a yellow organic pigment, and a purple organic pigment.
(3) Contains a red organic pigment, a yellow organic pigment, and a blue organic pigment.
(4) Contains a red organic pigment, a yellow organic pigment, and a green organic pigment.
(5) Contains a yellow organic pigment, a blue organic pigment, and a purple organic pigment.
(6) Contains a red organic pigment, a yellow organic pigment, a blue organic pigment, and a violet organic pigment.

As a specific example of the aspect (1) above, as a yellow organic pigment, C.I. I. Pigment Yellow 139, 185, 231, 233, and C.I. Pigment Yellow as a purple organic pigment. I. Pigment Violet 23.
As a specific example of the aspect (2) above, as a red organic pigment, C.I. I. Pigment Red 177, 254, 291, 295, 296, and C.I. pigment red as a yellow organic pigment. I. Pigment Yellow 139, 185, 231, 233, and C.I. Pigment Yellow as a purple organic pigment. I. Pigment Violet 23.
As a specific example of the aspect (3) above, as a red organic pigment, C.I. I. Pigment Red 177, 254, 291, 295, 296, and C.I. pigment red as a yellow organic pigment. I. Pigment Yellow 139, 185, 231, 233, and C.I. Pigment Yellow as a blue organic pigment. I. Pigment Blue 15:3, 15:4, and 15:6.
As a specific example of the aspect (4) above, as a red organic pigment, C.I. I. Pigment Red 177, 254, 291, 295, 296, and C.I. pigment red as a yellow organic pigment. I. Pigment Yellow 139, 185, 231, 233 and C.I. Pigment Yellow 139, 185, 231, 233 as a green organic pigment. I. Pigment Green 7, 36, 58, 59, and 63.
As a specific example of the aspect (5) above, as a yellow organic pigment, C.I. I. Pigment Yellow 139, 185, 231, 233, and C.I. Pigment Yellow as a blue organic pigment. I. Pigment Blue 15:3, 15:4, 15:6, and C.I. Pigment Blue as a purple organic pigment. I. Pigment Violet 23.
As a specific example of the aspect (6) above, as a red organic pigment, C.I. I. Pigment Red 177, 254, 291, 295, 296, and C.I. pigment red as a yellow organic pigment. I. Pigment Yellow 139, 185, 231, 233, and C.I. Pigment Yellow as a blue organic pigment. I. Pigment Blue 15:3, 15:4, 15:6, and C.I. Pigment Blue as a purple organic pigment. I. Pigment Violet 23.

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

Among the embodiments of (5) above, as the yellow organic pigment, C.I. I. Pigment Yellow 139 and C.I. as a blue organic pigment. I. Pigment Blue 15:6 and C.I. as a purple organic pigment. I. Pigment Violet 23 is more preferably contained.

Table 1 shows the preferred mass ratio (% by mass) of each organic pigment in each embodiment.

(Other colorants)
The photosensitive coloring composition of the present invention can contain colorants other than the black colorant (A).

Other colorants are not particularly limited, and organic pigments, inorganic pigments, and dyes can be appropriately selected and used.

Examples of organic pigments include compounds classified as pigments in the color index. Specifically, C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3,57,57:1,57:2,58:4,60,63,63:1,63:2,64,64:1,
68, 69, 81, 81: 1, 81: 2, 81: 3, 81: 4, 83, 88, 90: 1, 101, 101: 1, 104, 108, 108: 1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275,276,277,278,279,280,281,282,283,284,285,286,287, pigments described in JP 2014-134712, pigments described in Japanese Patent No. 6368844, etc. red organic pigment;
C. I. Orange organic pigments such as Pigment Orange 36, 38, 43, 62, 64, 71, 73;
C. I. Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 12, 13, 14, 15, 16, 17, 18, 24, 31, 32, 34, 35, 35: 1, 36, 36: 1, 37, 37: 1, 40, 42, 43, 53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 93, 94, 95, 97, 98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117, 118, 119, 120, 123, 126, 127, 128, 129, 138, 147, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167, 168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181, 182, 187, 188, 192, 193, 194,196,198,199,213,214, yellow organic pigments such as the pigments described in JP 2012-226110A;
C. I. Pigment Green 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 37, 45, 48, 50, 51, 54, 55, 58, 59, 62, Green organic pigment such as 63;
C. I. 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, Blue organic pigments such as 61,61:1,62,63,66,67,68,71,72,73,74,75,76,78,79;
C. I. 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, Violet organic pigments such as 39, 42, 44, 47, 49, 50, etc. are mentioned.

Examples of inorganic pigments include titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine blue, deep blue, chromium oxide green, cobalt green, amber, etc. can be mentioned.

Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Further, derivatives thereof, lake forms of dyes, and salt-forming compounds may be used.

The content of the black colorant (A) is preferably 5 to 70% by weight, more preferably 10 to 60% by weight based on 100% by weight of the nonvolatile content of the photosensitive coloring composition, from the viewpoint of light-shielding properties.

(Refining of pigment)
It is preferable to use the pigment in a finely divided form. The refinement method is not particularly limited, and, for example, any of wet milling, dry milling, and dissolution precipitation methods 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. Note that from the viewpoint of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

Salt milling is a process in which a mixture of pigments, water-soluble inorganic salts, and water-soluble organic solvents is mechanically heated while being heated using a kneader such as a kneader, two-roll mill, three-roll mill, ball mill, attriter, or sand mill. After kneading, water-soluble inorganic salts and water-soluble organic solvents are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the high hardness of the inorganic salt is used to crush the pigment during salt milling. By optimizing the conditions for salt milling pigments, it is possible to obtain pigments with very fine primary particle diameters, narrow distribution widths, and sharp particle size distributions.

Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, sodium sulfate, etc., and sodium chloride (salt) is preferred from the viewpoint of cost. The amount of water-soluble inorganic salt used is preferably 50 to 2,000 parts by weight, more preferably 300 to 1,000 parts by weight, based on 100 parts by weight of the pigment, from the viewpoint of both processing efficiency and production efficiency.

The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, a high boiling point solvent with a boiling point of 120° C. or higher is preferred from the viewpoint of safety. For example, 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, liquid polypropylene glycol, etc. are used. The amount of the 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.

A resin may be added to the salt milling treatment if necessary. 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, it is preferably solid at room temperature, insoluble in water, and partially soluble in the above organic solvent. The amount of resin added is preferably 2 to 200 parts by weight per 100 parts by weight of the pigment.

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

The dispersion resin (B) is preferably a resin having adsorption groups with high affinity for the black colorant (A). It is preferable that the adsorption group has either a basic group or an acidic group, and from the viewpoint of developability and pattern formation, it is more preferable that the adsorption group contains a dispersion resin (B1) having an acidic group.

Examples of acidic groups include carboxyl groups, phosphoric acid groups, and sulfonic acid groups. Among these, from the viewpoint of developability, carboxyl groups and phosphoric acid groups are preferred, and carboxyl groups are more preferred.

(Dispersed resin with acidic group (B1))
It is preferable that the dispersion resin (B) contains the dispersion resin (B1) having an acidic group from the viewpoint of developability and pattern forming properties. Examples of the dispersion resin (B1) having an acidic group include the following dispersion resins (B1-1) and (B1-2).

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

The tetracarboxylic dianhydride is, for example, 1,2,3,4-butanetetracarboxylic dianhydride, 1,2,3,4-cyclobutanetetracarboxylic dianhydride, 1,3-dimethyl-1 , 2,3,4-cyclobutanetetracarboxylic dianhydride, 1,2,3,4-cyclopentanetetracarboxylic dianhydride, 2,3,5-tricarboxycyclopentyl acetic acid dianhydride, 3,5, 6-tricarboxynorbornane-2-acetic dianhydride, 2,3,4,5-tetrahydrofurantetracarboxylic dianhydride, 5-(2,5-dioxotetrahydrofural)-3-methyl-3-cyclohexene- Aliphatic tetracarboxylic dianhydride such as 1,2-dicarboxylic dianhydride, bicyclo[2.2.2]-oct-7-ene-2,3,5,6-tetracarboxylic dianhydride, Pyromellitic dianhydride, ethylene glycol dianhydride trimellitic acid ester, propylene glycol dianhydride trimellitic acid ester, butylene glycol dianhydride trimellitic acid ester, 3,3',4,4'-benzophenonetetracarboxylic dianhydride 3,3',4,4'-biphenylsulfonetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride Anhydride, 3,3',4,4'-biphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-dimethyldiphenylsilane tetracarboxylic dianhydride, 3,3',4,4 '-Tetraphenylsilane tetracarboxylic dianhydride, 1,2,3,4-furantetracarboxylic dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylsulfide dianhydride, 4 , 4'-bis(3,4-dicarboxyphenoxy)diphenylsulfone dianhydride, 4,4'-bis(3,4-dicarboxyphenoxy)diphenylpropane dianhydride, 3,3',4,4' -Perfluoroisopropylidene diphthalic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, bis(phthalic acid) phenylphosphine oxide dianhydride, p-phenylene-bis(triphenyl phthalic acid) dianhydride, m-phenylene-bis(triphenylphthalic acid) dianhydride, bis(triphenylphthalic acid)-4,4'-diphenyl ether dianhydride, bis(triphenylphthalic acid)-4, 4'-diphenylmethane dianhydride, 9,9-bis(3,4-dicarboxyphenyl)fluorene dianhydride, 9,9-bis[4-(3,4-dicarboxyphenoxy)
phenyl]fluorene dianhydride, 3,4-dicarboxy-1,2,3,4-tetrahydro-1-naphthalenesuccinic dianhydride, or 3,4-dicarboxy-1,2,3,4-tetrahydro Examples include aromatic tetracarboxylic dianhydrides such as -6-methyl-1-naphthalenesuccinic dianhydride. Among these, aromatic tetracarboxylic dianhydrides are preferred from the viewpoint of adsorption to pigments.

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 dianhydride forms a dispersion resin having two carboxyl groups per unit of tetracarboxylic dianhydride through reaction with a hydroxyl group-containing compound, so from the viewpoint of pigment adsorption, the dispersion of the present invention is It is preferable as a constituent element of resin.

Examples of the tricarboxylic anhydride include aliphatic tricarboxylic anhydride, aromatic tricarboxylic anhydride, and the like.

The aliphatic tricarboxylic acid anhydride is, for example, 3-carboxymethylglutaric anhydride, 1,2,4-butanetricarboxylic acid-1,2-anhydride, cis-propene-1,2,3-tricarboxylic acid- Examples include 1,2-anhydride and 1,3,4-cyclopentanetricarboxylic anhydride.

The aromatic tricarboxylic acid is, for example, benzenetricarboxylic anhydride (1,2,3-benzenetricarboxylic anhydride, trimellitic anhydride [1,2,4-benzenetricarboxylic anhydride], etc.), naphthalene tricarboxylic anhydride, etc. Acid anhydride (1,2,4-naphthalenetricarboxylic anhydride, 1,4,5-naphthalenetricarboxylic anhydride, 2,3,6-naphthalenetricarboxylic anhydride, 1,2,8-naphthalenetricarboxylic anhydride) 3,4,4'-benzophenonetricarboxylic anhydride, 3,4,4'-biphenyl ethertricarboxylic anhydride, 3,4,4'-biphenyltricarboxylic anhydride, 2,3,2' -biphenyltricarboxylic anhydride, 3,4,4'-biphenylmethanetricarboxylic anhydride, and 3,4,4'-biphenylsulfonetricarboxylic anhydride. Among these, aromatic tricarboxylic acid anhydrides are preferred from the viewpoint of adsorption to pigments.

The molar ratio of the acid anhydride group in one or more acid anhydrides selected from the tetracarboxylic anhydride and tricarboxylic anhydride to the hydroxyl group in the hydroxyl group-containing compound is acid anhydride group/hydroxyl group = 0.5. ~1.5 is preferred. When the reaction is carried out at an appropriate ratio, it is easy to obtain a dispersed resin with good dispersibility.

Among monools and polyols, the hydroxyl group-containing compound is preferably a polyol such as a diol having a plurality of hydroxyl groups. The hydroxyl group in the polyol functions as a bonding point with the vinyl polymer moiety.
Examples of the polyol that serves as a bonding point with the vinyl polymer portion include at least one hydroxyl group-containing compound selected from the group of compounds having two hydroxyl groups and one thiol group in the molecule and vinyl polymers containing a hydroxyl group at one end. . For example, 1-mercapto-1,1-methanediol, 1-mercapto-1,1-ethanediol, 3-mercapto-1,2-propanediol (thioglycerin or 1-thioglycerol), 2-mercapto-1,
2-propanediol, 2-mercapto-2-methyl-1,3-propanediol, 2-mercapto-2-ethyl-1,3-propanediol, 1-mercapto-2,2-propanediol, 2-mercaptoethyl -2-methyl-1,3-propanediol, 2-mercaptoethyl-2-ethyl-1,3-propanediol, and the like.

Examples of the dispersion resin (B1-1) having an acidic group include the following (B1-1-1) or (B1-1-2).

≪Dispersion resin having acidic group (B1-1-1)≫
The vinyl polymer moiety of the dispersion resin (B1-1-1) having an acidic group has at least one thermally crosslinkable type selected from the group consisting of (i) a hydroxyl group, an oxetane group, a t-butyl group, and a blocked isocyanate group. It is obtained by radical polymerization of a monomer having a group, (ii) a carboxyl group-containing monomer, and, if necessary, (iii) another monomer.

(i-1) [Hydroxy group-containing monomer]
The monomer having a hydroxyl group as a thermally crosslinkable group is a (meth)acrylate monomer having a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate, 2 (or 3)-hydroxypropyl (meth)acrylate, 2 (or 3 or 4)-hydroxyalkyl (meth)acrylates such as hydroxybutyl (meth)acrylate and cyclohexanedimethanol mono(meth)acrylate, and alkyl-α-hydroxyalkyl acrylates such as ethyl-α-hydroxymethyl acrylate;
Alternatively, a (meth)acrylamide monomer having a hydroxyl group, such as N-(2-hydroxyethyl)(meth)acrylamide, N-(2-hydroxypropyl)(meth)acrylamide, N-(2-hydroxybutyl)( N-(hydroxyalkyl)(meth)acrylamide such as 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, 2-(or 3- or 4-) hydroxybutyl vinyl ether,
Or an allyl ether monomer having a hydroxyl group, for example, hydroxyalkyl such as 2-hydroxyethyl allyl ether, 2-(or 3-) hydroxypropyl allyl ether, 2-(or 3- or 4-) hydroxybutyl allyl ether, etc. Examples include allyl ether.

It can also be obtained by adding alkylene oxide and/or lactone to the above-mentioned hydroxyalkyl (meth)acrylate, alkyl-α-hydroxyalkyl acrylate, N-(hydroxyalkyl)(meth)acrylamide, hydroxyalkyl vinyl ether or hydroxyalkyl allyl ether. Also preferred are monomers such as The alkylene oxide to be added includes, for example, ethylene oxide, propylene oxide, 1,2-, 1,4-, 2,3- or 1,3-butylene oxide, and a combination system of two or more of these. When two or more types of alkylene oxides are used together, the bonding format may be either random or block. The lactone to be added includes, for example, δ-valerolactone, ε-caprolactone, ε-caprolactone substituted with an alkyl group having 1 to 6 carbon atoms, and a combination system of two or more of these. It is also possible to add both alkylene oxide and lactone.

(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 them, (3-ethyloxetan-3-yl)methyl methacrylate and the like are preferred. Commercially available products include, for example, ETE
RNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate)
(manufactured by Ube Industries).

(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.

(i-4) [Blocked isocyanate group-containing monomer]
Monomers having a blocked isocyanate group as a thermally crosslinkable group include 2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate, 2-[(3,5-dimethylpyrazolyl)carbonylamino] Examples include ethyl methacrylate. Commercially available products include, for example, Karenz MOI-BM (2-(0-[1'-methylpropylideneamino]carboxyamino)ethyl methacrylate) (manufactured by Showa Denko), Karenz MOI-BP (2-[(
3,5-dimethylpyrazolyl)carbonylamino]ethyl methacrylate (manufactured by Showa Denko).

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, preferably 20 to 60% by mass in the total monomers. preferable. If it is 5% by mass or more, it is possible to obtain a photosensitive coloring composition with excellent resistance 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.

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

(iii) [Other monomers]
For the vinyl polymer portion of the acidic group-containing dispersion resin (B1-1-1), other monomers than the thermally crosslinkable monomer and the carboxyl group-containing monomer can be used.
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, 2 - Alkyl (meth)acrylates such as ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate;
Aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, 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)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, acryloylmorpholine, etc. Acrylamides;
Amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate;
and nitriles such as (meth)acrylonitrile.

Also included are 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 fatty acid vinyls such as vinyl acetate and vinyl propionate. .

≪Dispersion resin having acidic group (B1-1-2)≫
The dispersion resin (B1-1-2) having an acidic group has a polymerizable unsaturated group in the vinyl polymer portion.

The method for producing the dispersion resin (B1-1-2) having an acidic group includes, for example, a compound having a (meth)acryloyl group, which is a polymerizable unsaturated group, and a functional group, and a compound containing a functional group that reacts with the functional group. It can be obtained by reacting a monomer containing a monomer with a polymer. Examples include a reaction product of glycidyl methacrylate and a polymer having a hydroxyl group or a carboxyl group, a reaction product of methacryloyloxyethyl isocyanate and a polymer having a hydroxyl group or a carboxyl group, and the like.
A polymer having a hydroxyl group or a carboxyl group can also be obtained by subjecting a polymer having a glycidyl group to a ring-opening reaction with an acid anhydride compound, or by subjecting a polymer having an acid anhydride group to a ring-opening reaction. For example, the dispersion resin described in JP-A No. 2011-157416 can be mentioned.

[Dispersion resin with acidic group (B1-2)]
The dispersion resin (B1-2) having an acidic group is a dispersion resin represented by the following general formula (2), and specifically, it is a dispersion resin described in JP-A No. 2007-140487.

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

The acid value of the dispersion resin (B1) having an acidic group is preferably 20 to 250 mgKOH/g, more preferably 30 to 200 mgKOH/g, from the viewpoint of developability and pattern formation.

The dispersion resin (B1) having an acidic group can be used alone or in combination of two or more types.

The content of the dispersion resin (B1) having an acidic group is preferably 3 to 200 parts by mass, and 5 to 100 parts by mass, based on 100 parts by mass of the black colorant (A) from the viewpoint of developability and pattern formation. is more preferable.

(Dispersed resin (B2) other than (B1))
The photosensitive coloring composition of the present invention can contain, as the dispersion resin (B), a dispersion resin (B2) (hereinafter also referred to as other dispersion resin (B2)) other than the dispersion resin (B1) having an acidic group.

Other dispersion resins (B2) are not particularly limited, and known dispersion resins can be used. Among these, a basic dispersion resin is preferred from the viewpoint of dispersion stability.

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

Other dispersion resins (B2) include, for example, Disperbyk-2000, 2001, 2009, 2010, 2020, 2025, 2050, 2070, 2095, 2150, 2155, 2163, 2164 manufactured by BYK Chemie Japan; SOLSPERSE-20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 530 95, 55000, 56000, 76500, etc., manufactured by BASF EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330 Ajisuper manufactured by Ajinomoto Fine Techno Co., Ltd. Examples include PA111, PB711, PB821, PB822, PB824, and the like. Further, examples include dispersion resins described in JP-A No. 2004-182787, JP-A No. 2013-119568, JP-A No. 2017-019937, JP-A No. 2018-172530, and the like.

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

The polymerizable compound (C) is not particularly limited, and known compounds that can be crosslinked by radicals, acids, or heat can be used, and include monomers (monomers) containing polymerizable unsaturated groups, dimers, trimers and oligomers. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group.

(Polymerizable compound (C1) having a urethane bond)
The photosensitive coloring composition of the present invention preferably contains a polymerizable compound (C1) having a urethane bond as the polymerizable compound (C) from the viewpoint of suppressing wrinkles and pattern forming properties. Furthermore, desired photocurability can be obtained even with a film containing the black colorant (A).

The polymerizable compound (C1) having a urethane bond is, for example, a urethane (meth)acrylate obtained by reacting a polyfunctional isocyanate with a (meth)acrylate having a hydroxyl group, or a polyfunctional isocyanate obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate. Examples include urethane (meth)acrylate obtained by reacting (meth)acrylate having a hydroxyl group.

The above-mentioned (meth)acrylate having a hydroxyl group is, for example, 2-hydroxyethyl (meth)
Acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene Oxide-modified penta(meth)acrylate, dipentaerythritol propylene oxide-modified penta(meth)acrylate, dipentaerythritol caprolactone-modified penta(meth)acrylate, glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, epoxy Examples include reaction products of group-containing compounds and carboxy (meth)acrylates, hydroxyl group-containing polyol polyacrylates, and the like.

Examples of the polyfunctional isocyanates include aromatic diisocyanates such as tolylene diisocyanate, diphenylmethylene diisocyanate, and xylene diisocyanate, aliphatic diisocyanates such as trimethylene diisocyanate, tetramethylene diisocyanate, and hexamethylene diisocyanate, and alicyclic diisocyanate such as isophorone diisocyanate. , their burette bodies, isocyanate nurate bodies, trimethylolpropane adducts, and the like.

The polymerizable compound (C1) having a urethane bond preferably has an acid group from the viewpoint of developability. Examples of acid groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups. Among these, a carboxyl group is preferred.

As a method for introducing an acid group into the polymerizable compound (C1) having a urethane bond, for example, first, the above-mentioned (meth)acrylate having a hydroxyl group and the above-mentioned polyfunctional isocyanate are reacted. Next, it can be synthesized by adding a mercapto compound having a carboxyl group to the product.

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

The number of polymerizable unsaturated groups in the polymerizable compound (C1) having a urethane bond is preferably 3 to 15, more preferably 5 to 12, from the viewpoint of wrinkle suppression and pattern formation.

The molecular weight of the polymerizable compound (C1) having a urethane bond is preferably 500 to 5,000, more preferably 500 to 3,000, from the viewpoint of wrinkle suppression and pattern formation.

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

The content of the polymerizable compound (C1) having a urethane bond is preferably 10 to 100% by mass, and preferably 20 to 100% by mass based on 100% by mass of the polymerizable compound (C) from the viewpoint of suppressing wrinkles and pattern forming properties. More preferably, it is 80% by mass.

(Polymerizable compound (C2) other than (C1))
The photosensitive coloring composition of the present invention contains a polymerizable compound (C2) other than (C1) (hereinafter also referred to as other polymerizable compound (C2)) from the viewpoint of wrinkle suppression, developability, and pattern formation. It is preferable to include.

Other polymerizable compounds (C2) include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxylic Ethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 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, isocyanuric acid EO modified tri(meth)acrylate Acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di( meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, methylolated melamine ( Various acrylic esters and methacrylic esters such as meth)acrylic esters and epoxy(meth)acrylates, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl Examples include (meth)acrylamide, N-vinylformamide, acrylonitrile, and the like. Among these, (meth)acrylates having an acid group, lactone-modified (meth)acrylates, and (meth)acrylates having a cardo structure are preferred, and (meth)acrylates having a cardo structure are more preferred from the viewpoint of suppressing wrinkles.

Other commercially available polymerizable compounds (C2) include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604 manufactured by Nippon Kayaku Co., Ltd. , R-684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, DPCA-2
0, DPCA-30, DPCA-60, DPCA-120, Aronix M-303, M-305, M-306, M-309, M-310, M-321, M-325, M- manufactured by Toagosei Co., Ltd. 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 manufactured by Osaka Gas Chemical Co., Ltd. , GA-2800, Miwon Specialty Chemical Co. , Ltd. Miramer HR6060, 6100, 6200, Osaka Organic Co., Ltd. Viscoat #2500P, Shin-Nakamura Chemical Co., Ltd. NK Ester ABE-300, A-DOG, A-DCP, A-BPE-4, Daicel. Examples include EBECRY40, 130, 140, and 145 manufactured by Allnex Corporation.

Commercially available (meth)acrylates having acid groups include, for example, Viscoat #2500P manufactured by Osaka Organic Co., Ltd., Aronix M-5300, M-5400, M-5700, M-510, M-520, and M manufactured by Toagosei Co., Ltd. -521 etc. are mentioned.

Examples of commercially available lactone-modified (meth)acrylates include KAYARAD DPCA-20, 30, 60, and 120 manufactured by Nippon Kayaku Co., Ltd.

Commercially available (meth)acrylates having a cardo structure are, for example, OGSOL EA-0200, 0300 manufactured by Osaka Gas Chemical Co., Ltd., and Miwon Specialty Chemical Co., Ltd. , Ltd. Miramer HR6060, 6100, 6200, and the like.

Other polymerizable compounds (C2) can be used alone or in combination of two or more.

The content of the polymerizable compound (C) is preferably 1 to 60% by weight, more preferably 2 to 50% by weight based on 100% by weight of nonvolatile content of the photosensitive coloring composition.

[Photopolymerization initiator (D)]
The photosensitive coloring composition of the present invention contains an oxime-based photopolymerization initiator (D1) represented by general formula (1) as a photopolymerization initiator (D).

(Oxime photopolymerization initiator (D1))
The oxime photopolymerization initiator (D1) is a compound represented by the following general formula (1).
General formula (1)


(In general formula (1), R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or Represents 2 to 20 heterocyclic groups.
R ₂ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₃ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₄ represents any monovalent substituent. n represents an integer from 0 to 3. )

R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. represent.
The alkyl group having 1 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof; for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group. group, isobutyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group , hexadecyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, and the like.
Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, and anthryl group.
Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, and phenylethyl group.
Examples of the heterocyclic group having 2 to 20 carbon atoms include pyridyl group, pyrimidyl group, furyl group, tetrahydrofuryl group, dioxolanyl group, imidazolidyl group, oxazolidyl group, piperidyl group, and morpholinyl group.
Among the above, from the viewpoint of reactivity, a methyl group, an ethyl group, or a phenyl group is preferable, and a methyl group or an ethyl group is more preferable.

R ₂ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
The alkyl group having 3 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof; for example, propyl group, isopropyl group, butyl group, isobutyl group, t -Butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group , cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, and the like.
Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, and anthryl group.
Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, and phenylethyl group.
Examples of the heterocyclic group having 2 to 20 carbon atoms include pyridyl group, pyrimidyl group, furyl group, tetrahydrofuryl group, dioxolanyl group, imidazolidyl group, oxazolidyl group, piperidyl group, and morpholinyl group.
Among the above, from the viewpoint of pattern forming properties, alkyl groups having 3 to 20 carbon atoms are preferred, alkyl groups having 3 to 8 carbon atoms are more preferred, and pentyl groups are particularly preferred.

R ₃ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
The alkyl group having 3 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof; for example, propyl group, isopropyl group, butyl group, isobutyl group, t -butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group,
Examples include isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, and cyclohexylmethyl group.
Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, and anthryl group.
Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, and phenylethyl group.
Examples of the heterocyclic group having 2 to 20 carbon atoms include pyridyl group, pyrimidyl group, furyl group, tetrahydrofuryl group, dioxolanyl group, imidazolidyl group, oxazolidyl group, piperidyl group, and morpholinyl group.
Among the above, from the viewpoint of pattern formation, branched alkyl groups having 3 to 15 carbon atoms are preferable, branched alkyl groups having 5 to 12 carbon atoms are more preferable, 3-methylbutyl group, 2-ethylhexyl group, etc. Particularly preferred are groups.

R ₄ represents any monovalent substituent.
As arbitrary monovalent substituents, alkyl groups having 1 to 20 carbon atoms such as methyl group and ethyl group; alkoxy groups having 1 to 20 carbon atoms such as methoxy group and ethoxy group; F, Cl, Br, Halogen atoms such as I; acyl groups having 1 to 20 carbon atoms; alkyl ester groups having 1 to 20 carbon atoms; alkoxycarbonyl groups having 1 to 20 carbon atoms; halogenated alkyl groups having 1 to 20 carbon atoms; Aromatic ring group having 4 to 20 carbon atoms; Amino group; Aminoalkyl group having 1 to 20 carbon atoms; Hydroxyl group; Nitro group; Cyano group; Benzoyl group which may have a substituent; Good examples include thenoyl group. Examples of substituents that the benzoyl group or thenoyl group may have include an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an alkoxycarbonyl group having 1 to 10 carbon atoms, etc. , in the range of 1 to 3.
Among the above, from the viewpoint of reactivity, a benzoyl group which may have a substituent is preferable, and a benzoyl group whose substituent is an alkoxycarbonyl group is more preferable.

In general formula (1), n represents an integer of 0 to 3.
From the viewpoint of radical generation efficiency, it is preferably 0 or 1, and more preferably 1.

The method for producing the oxime photopolymerization initiator (D1) is not particularly limited, and any known method can be used. For example, methods described in International Publication No. 2008/078678, International Publication No. 2014/050738, Japanese Patent Application Publication No. 2016-519675, etc. can be used.

Specific examples of the compound represented by general formula (1) are shown below. Note that the present invention is not limited to these.

Among the compounds of chemical formulas (3) to (8), the compound of chemical formula (8) is preferred from the viewpoint of wrinkle suppression and pattern forming properties.

The oxime photopolymerization initiator (D1) can be used alone or in combination of two or more types.

The content of the oxime-based photopolymerization initiator (D1) is preferably 10 to 100% by mass, more preferably 30 to 90% by mass based on 100% by mass of the photopolymerization initiator (D).

(Photopolymerization initiator (D2) other than (D1))
From the viewpoint of developability and pattern formation, the photopolymerization initiator (D) is a photopolymerization initiator (D2) other than the oxime photoinitiator (D1) represented by the general formula (1) (hereinafter referred to as "other"). It is preferable to include a photopolymerization initiator (also referred to as a photopolymerization initiator (D2)).

Other photopolymerization initiators (D2) are not particularly limited as long as they are compounds that can initiate polymerization of the polymerizable compound (C) with light, and any known photopolymerization initiators can be used.

The photopolymerization initiator (D2) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1- one, 1-hydroxycyclohexyl phenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4-morpholino) ) phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1- Acetophenone photopolymerization initiator such as butanone;
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl -A benzophenone photopolymerization initiator such as 4'-methyldiphenyl sulfide or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone;
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)-triazine methyl)-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. photopolymerizable initiator;
Initiation of photopolymerization of acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or diphenyl-2,4,6-trimethylbenzoylphosphine oxide agent;
1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)], or ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole An oxime photopolymerization initiator other than the oxime photopolymerization initiator (D1) such as 3-yl]-,1-(O-acetyloxime);
2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl))4,4',5,5'- Tetraphenylbiimidazole, 2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4' , 5,5'-tetra(m-methoxyphenyl)biididazole, 2,2'-bis(o,o'-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'- Bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole , 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole and other imidazole-based photopolymerization initiators.
Among these, from the viewpoint of developability and pattern formation, oxime-based photopolymerization initiators other than acetophenone-based photopolymerization initiators, acylphosphine oxide-based polymerization initiators, and oxime-based photopolymerization initiators (D1) are preferred. .

Commercially available acetophenone photopolymerization initiators include Omnirad 907, 369, and 379EG manufactured by IGM Resins.
Commercially available acylphosphine oxide polymerization initiators include Omnirad 819 and TPO manufactured by IGM Resins.
Commercially available oxime photopolymerization initiators other than oxime photopolymerization initiator (D1) include IRGACURE OXE-01, 02, 03, 04 manufactured by BASF, and ADEKA ARCURE N-1919 and NCI manufactured by ADEKA. -730,831,930, TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 358, 380, 365, 610, 3054, 3057 manufactured by Changzhou Strong New Materials Company, OMNIRAD1312 manufactured by IGM Resins Company, 1314, 1316, SPI-02, 03, 04, 05, 06, 07 manufactured by Samyang Corporation, DFI-020, 306, EOX-01 manufactured by Daito Chemix, etc.

The photopolymerization initiator (D2) can be used alone or in combination of two or more types.

The content of the photopolymerization initiator (D) is preferably 2 to 50 parts by mass, more preferably 2 to 30 parts by mass, from the viewpoint of photocurability and developability, based on 100 parts by mass of the black colorant (A). preferable.

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

The binder resin (E) is not particularly limited, and any known resin can be used.

The binder resin (E) can be classified into non-photosensitive binder resins and photosensitive binder resins, and preferably has an alkali-soluble group from the viewpoint of developability. Examples of the alkali-soluble group include a carboxyl group, a phosphoric acid group, a sulfonic acid group, a hydroxyl group, a phenolic hydroxyl group, and among these, a carboxyl group is preferred.
Further, the binder resin (E) can contain a thermosetting group such as an epoxy group or an oxetanyl group.

(Non-photosensitive binder resin)
The non-photosensitive binder resin is, for example, an acrylic resin having an acidic group, an α-olefin/(anhydride) maleic acid copolymer, a styrene/styrene sulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or Examples include isobutylene/(anhydrous) maleic acid copolymer. Among these, acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers are preferred.

(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 method (i) or (ii) shown below, for example. When cured with active energy rays, the resin undergoes three-dimensional crosslinking, improving crosslinking density and improving chemical resistance.

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

Epoxy group-containing monomers include, for example, glycidyl (meth)acrylate, methylglycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4- Epoxycyclohexyl (meth)acrylate is mentioned. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity.

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 Acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethylene oxide (EO) modified cresol acrylate, n-nonyl Phenoxypolyethylene 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, nonylphenol (meth)acrylates such as PO-modified (meth)acrylate;
(Meth)acrylamides such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, or acryloylmorpholine. ;
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;
Fatty acid vinyls 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'-bismaleimidiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene di Maleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, 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 N-substituted maleimides such as -6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine;
2-(meth)acryloyloxyethyl acid phosphate, a phosphoric acid ester group-containing monomer such as a compound in which a phosphoric acid esterification agent such as phosphorus pentoxide or polyphosphoric acid is reacted with the hydroxyl group of a hydroxyl group-containing monomer described below. Examples include mercury.

Examples of monocarboxyl group-containing monomers include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, and haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted α-positions of (meth)acrylic acid. Examples include monocarboxylic acids such as carboxylic acid and the like.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like. Further, if necessary, the remaining anhydride group can be hydrolyzed using a tricarboxylic dianhydride such as trimellitic anhydride or a tetracarboxylic dianhydride such as pyromellitic anhydride.

Further, as a method similar to method (i), for example, a polymer of a carboxyl group-containing monomer and other monomers is synthesized. Next, a method of obtaining a photosensitive binder resin by adding an epoxy group-containing monomer to a portion of the carboxyl groups of the polymer may be mentioned.

[Method (ii)]
In method (ii), for example, a polymer of a hydroxyl group-containing monomer, a monocarboxyl group-containing monomer, and other monomers is synthesized. Next, a method may be mentioned in which the hydroxyl groups of the polymer are reacted with the isocyanate groups of an isocyanate group-containing monomer.

Hydroxyl group-containing monomers include, for example, 2-hydroxyethyl (meth)acrylate, 2- or 3-hydroxypropyl (meth)acrylate, 2-, 3- or 4-hydroxybutyl (meth)acrylate, glycerol mono(meth)acrylate, Examples include acrylates and hydroxyalkyl methacrylates such as cyclohexanedimethanol mono(meth)acrylate. In addition, polyether mono(meth)acrylate obtained by addition polymerizing ethylene oxide, propylene oxide, and/or butylene oxide, etc. to hydroxyalkyl (meth)acrylate, polyγ-valerolactone, polyε-caprolactone, and/or polyester Also included are polyester mono(meth)acrylates to which 12-hydroxystearic acid and the like are added. Among these, 2-hydroxyethyl methacrylate and glycerol mono(meth)acrylate are preferred because they are less likely to cause foreign matter in the coating. Further, from the viewpoint of photosensitivity, glycerol mono(meth)acrylate is preferable.

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

As the monocarboxyl group-containing monomer and other monomers, those mentioned above can be used.

The raw materials used for synthesizing the photosensitive binder resin can be used alone or in combination of two or more.

Binder resin (E) can be used alone or in combination of two or more types.

From the viewpoint of developability, the weight average molecular weight (Mw) of the binder resin (E) is preferably 2,000 to 40,000, more preferably 3,000 to 300,00, and even more preferably 4,000 to 20,000. preferable. Moreover, the value of Mw/Mn is preferably 10 or less. A suitable weight average molecular weight (Mw) improves adhesion to the substrate and developability.

The acid value of the binder resin (E) is preferably 50 to 200 mgKOH/g, more preferably 70 to 180 mgKOH/g, and even more preferably 90 to 170 mgKOH/g. Appropriate acid value improves adhesion to the substrate and developability.

The content of the binder resin (E) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on 100 parts by mass of the black colorant (A).

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

The dye derivative (F) is not particularly limited, and includes dye derivatives having an acidic group, a basic group, a neutral group, etc. in the organic dye residue. The dye derivative (F) is, for example, a compound having an acidic substituent such as a sulfo group, a carboxy group, or a phosphoric acid group, or an amine salt thereof, or a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal. Examples include compounds having a neutral substituent such as a phenyl group or a phthalimido alkyl 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, and benzoisomer pigments. Examples include indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo.

Specifically, as diketopyrrolopyrrole dye derivatives, JP 2001-220520 A, WO 2009/081930, WO 2011/052617, WO 2012/102399, JP 2017 -156397, as phthalocyanine dye derivatives, JP 2007-226161, WO 2016/163351, JP 2017-165820, and Japanese Patent No. 5753266, as anthraquinone dye derivatives, JP-A-63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, International Publication No. 2009/025325, Quinacridone series Examples of dye derivatives include JP-A-48-54128, JP-A-03-9961, and JP-A-2000-273383; examples of dioxazine-based dye derivatives include JP-A-2011-162662; thiazine indigo dyes; Derivatives include JP 2007-314785, triazine dye derivatives include JP 61-246261, JP 11-199796, JP 2003-165922, and JP 2003-168208. Publications, JP 2004-217842, JP 2007-314681, benzisoindole dye derivatives, JP 2009-57478, quinophthalone dye derivatives, JP 2003-167112, JP 2006-291194, JP 2008-31281, JP 2012-226110, naphthol dye derivatives include JP 2012-208329, JP 2014-5439, and azo dyes. The derivatives are described in JP-A-2001-172520 and JP-A-2012-172092, the acidic substituent is in JP-A-2004-307854, and the basic substituent is in JP-A-2002-201377 and JP-A-2002-201377. Examples include known dye derivatives described in JP-A No. 2003-171594, JP-A No. 2005-181383, JP-A No. 2005-213404, and the like. In addition, in these documents, the dye derivative is sometimes described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound. A compound having a substituent such as a neutral group has the same meaning as a dye derivative.

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

The content of the dye derivative (F) is preferably 1 to 20 parts by weight, more preferably 2 to 10 parts by weight, based on 100 parts by weight of the black colorant (A).

[Near infrared absorber (G)]
The photosensitive coloring composition of the present invention preferably contains a near-infrared absorber (G) when used in a solid-state image sensor such as an infrared sensor. Thereby, it is possible to produce an infrared sensor that can block light in the visible light region, control the transmission of infrared rays of a specific wavelength, and suppress the generation of noise derived from visible light. The near-infrared absorber (G) is preferably a compound that absorbs light with a wavelength of 750 to 2,000 nm.

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

Cyanine compounds are disclosed in WO 2006/006573, WO 2010/073857, JP 2013-241598, JP 2016-113501, JP 2016-113504; 4-23868, JP 06-192584, JP 2000-63691, WO 2014/208514; Naphthalocyanine compounds are disclosed in JP 11-152414, JP 2000-86919. , JP 2009-29955 A, International Publication No. 2018/186490; Immonium compounds are JP 2005-336150 A, JP 2007-197492 A, JP 2008-88426 A; Pyrrolopyrrole compounds The squarylium compound is disclosed in JP2009-263614A, JP2010-90313A, JP2011-068731A; squarylium compound is JP2011-132361A, JP2016-142891A, WO2017 /135359, International Publication No. 2018/225837, JP2019-001987, International Publication No. 2020/054718; Examples of the croconium compound include compounds described in International Publication No. 2019/021767.

The near-infrared absorber (G) can be used alone or in combination of two or more.

The content of the near-infrared absorber (G) is preferably 10 to 200 parts by mass, and 15 to 150 parts by mass, based on 100 parts by mass of the black colorant (A), from the viewpoint of suppressing the generation of noise derived from visible light. parts by weight is more preferable, and 20 to 100 parts by weight is particularly preferable.

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

Examples of the sensitizer (H) include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, and naphthoquinone. Derivatives, polymethine dyes such as anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, oxonol derivatives, acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, squarylium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxaryloporphyrin derivatives Radin derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphylline derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, or Michler ketone derivatives, α-alpha Siloxy ester, acyl oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone, 4,4'-diethylisophthalophenone, 3,3' or 4,4'- Examples include tetra(t-butylperoxycarbonyl)benzophenone and 4,4'-bis(diethylamino)benzophenone.

Among the sensitizers (H), thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred. 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, 3,6-dibenzoyl- N-ethylcarbazole and the like are preferred.

The sensitizer (H) can be used alone or in combination of two or more.

The content of the sensitizer (H) is preferably 3 to 60 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the photopolymerization initiator (D). Containing an appropriate amount improves photocurability and developability.

[Thermosetting compound (I)]
The photosensitive coloring composition of the present invention can contain a thermosetting compound (I). Thereby, the thermosetting compound (I) reacts in the heating step, and the crosslinking density increases, so that the heat resistance improves.

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

(Epoxy compound (I1))
Epoxy compounds (I1) include, for example, bisphenols (bisphenol A, bisphenol F, bisphenol S, biphenol, bisphenol AD, etc.), phenols (phenol, alkyl-substituted phenol, aromatic-substituted phenol, naphthol, alkyl-substituted naphthol, dihydroxybenzene). , alkyl-substituted dihydroxybenzene, dihydroxynaphthalene, etc.) and various aldehydes (formaldehyde, acetaldehyde, alkyl aldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaraldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.). Polymerization of compounds, phenols, and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnorbornene, tetrahydroindene, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) polycondensates of phenols and ketones (acetone, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'- benzene dimethanol, biphenyl dimethanol, α, α, α', α'-biphenyl dimethanol, etc.), polycondensates of phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethyl biphenyl, etc.) etc.), polycondensates of bisphenols and various aldehydes, glycidyl ether epoxy resins obtained by glycidylating alcohols, etc., alicyclic epoxy resins, heterocyclic epoxy resins, aliphatic epoxy resins, glycidyl amines. Examples include glycidyl ester-based epoxy resins and glycidyl ester-based epoxy resins.

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

The content of the epoxy compound (I1) is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass, based on 100 parts by mass of the colorant (A) from the viewpoint of heat resistance of the cured film. .

(Oxetane compound (I2))
Oxetane compound (I2) is a known compound having an oxetane group. Examples of the oxetane compound include monofunctional oxetane compounds, bifunctional oxetane compounds, and trifunctional or more functional oxetane compounds.

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

Commercially available products include, for example, OXE-10,30 manufactured by Osaka Organic Chemical Industry Co., Ltd. and OXT-101,212 manufactured by Toagosei Co., Ltd.

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

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

Trifunctional or higher functional oxetane compounds include, for example, pentaerythritol tris(3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis(3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol hexa(3-ethyl-3 -oxetanylmethyl) ether, dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone modified dipentaerythritol hexa(3-ethyl- 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentakis (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropane tetrakis (3-ethyl-3-oxetanylmethyl) ether, oxetane group-containing resin ( Examples include polymers obtained by radical polymerization of (meth)acrylic monomers such as oxetane-modified phenol novolac resin described in Japanese Patent No. 3783462) and the above-mentioned OXE-30.

The content of the oxetane compound (I2) is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight based on 100% by weight of the nonvolatile content of the photosensitive coloring composition.

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

Commercially available products include, for example, Nikarak MW-30HM, MW-390, MW-100LM, MX-750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, manufactured by Sanwa Chemical Co., Ltd. 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, MX-410, and Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, and 370 manufactured by Nippon Cytec Industries.

Among these, Nikarak MW-30HM, MW-390, MW-100LM, and MX manufactured by Sanwa Chemical Co., Ltd. have an average number of methylol groups and/or ether groups per melamine ring of 5.0 or more. -750LM, MW-30M, MW-30, MW-22, MS-21, MS-11, MW-24X, MX-45, Cymel 232, 235, 236, 238, 300 manufactured by Nippon Cytec Industries, Ltd. , 301, 303, 350, etc. are preferable in that they can increase the crosslinking density.

The thermosetting compound (I) can be used alone or in combination of two or more types.

[Curing agent (curing accelerator)]
The photosensitive coloring composition of the present invention can be used in combination with a curing agent (curing accelerator) in order to assist in curing the thermosetting compound (I). Examples of the curing agent include amine compounds, acid anhydrides, active esters, carboxylic acid compounds, and sulfonic acid compounds. The curing agent is, for example, an amine compound (for example, 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, -Methylimidazole, 2-ethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 4-phenylimidazole, 1-cyanoethyl-2-phenylimidazole, 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.).

The curing agents can be used alone or in combination of two or more types.

The content of the curing agent is preferably 0.01 to 15 parts by mass based on 100 parts by mass of thermosetting compound (I).

[Thiol chain transfer agent (J)]
The photosensitive coloring composition of the present invention can contain a thiol chain transfer agent (J). When the thiol-based chain transfer agent (J) is used in combination with the photopolymerization initiator (D), thiyl radicals, which are less susceptible to polymerization inhibition by oxygen, are generated during radical polymerization after light irradiation, and the photosensitivity of the photosensitive coloring composition is reduced. improves.

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

Examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, and ethylene glycol bisthiopropionate. , trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, trimercapto Tris(2-hydroxyethyl)propionate isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto- Examples include s-triazine, and preferred examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

The thiol chain transfer agent (J) can be used alone or in combination of two or more types.

The content of the thiol chain transfer agent (J) is preferably 1 to 10 parts by weight, more preferably 2 to 8 parts by weight, based on 100 parts by weight of the nonvolatile content of the photosensitive coloring composition. When contained in an appropriate amount, photosensitivity is improved and wrinkles are less likely to occur on the surface of the cured film.

[Polymerization inhibitor (K)]
The photosensitive coloring composition of the present invention can contain a polymerization inhibitor (K).

Examples of the polymerization inhibitor (K) include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, and 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, alkylcatechol compounds such as 3,5-di-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2 - Alkylresorcinol compounds such as propylresorcinol, 4-propylresorcinol, 2-n-butylresorcinol, 4-n-butylresorcinol, 2-t-butylresorcinol, 4-t-butylresorcinol, Alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine, etc. , phosphine compounds such as trioctylphosphine oxide and triphenylphosphine oxide, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, and phloroglucin.

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

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

The ultraviolet absorber (L) is an organic compound having an ultraviolet absorption function, and includes 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. Examples include compounds.

Examples of benzotriazole compounds include 2-(5methyl-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-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'- Hydroxy-5'-t-octylphenyl)benzotriazole, 95% with 5% 2-methoxy-1-methylethyl acetate
benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1-dimethylethyl)-4-hydroxy, a mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazole) 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-benzotriazol2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol2-yl)-4-( 1,1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] , 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3,5 -di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3-tert- Butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5-chloro-2H -benzotriazol2-yl)phenyl]propionate.

Commercially available products include, for example, TINUVIN P, PS, 234, 326 manufactured by BASF Japan.
, 329, 384-2, 900, 928, 99-2, 1130, ADEKA STAB LA-29, LA-31RG, LA-32, LA-36, KEMISORB71, 73, 74, 79 manufactured by ChemiPro Kasei Co., Ltd. , 279, RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

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, 2-(2,4-dihydroxy Reaction product of phenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and (2-ethylhexyl)-glycidic acid ester, 2,4-bis(2-hydroxy-4 -butoxyphenyl"-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-( hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6- Examples include tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Commercially available products include, for example, KEMISORB 102 manufactured by ChemiPro Kasei Co., Ltd., and TINUVIN 400, 405, 460, 477, 479, 1577ED, and AD manufactured by BASF Japan.
Examples include ADK STAB LA-46 and LA-F70 manufactured by EKA, and CYASORB UV-1164 manufactured by Sun Chemical.

Examples of benzophenone compounds include 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3, 2-hydroxy-4-n-oct Xybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octa Desyloxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, etc. .

Commercially available products include, for example, KEMISORB 10, 11, 11S, 12 manufactured by ChemiPro Kasei Co., Ltd.
, 111, SEESORB 101, 107 manufactured by Shipro Kasei Co., Ltd., ADEKA STAB 1413 manufactured by ADEKA Co., Ltd., UV-12 manufactured by Sun Chemical Co., Ltd., and the like.

Examples of salicylic acid ester compounds include phenyl salicylate, p-octylphenyl salicylate, and p-tertbutylphenyl salicylate.

The content of the ultraviolet absorber (L) is preferably 5 to 70% by mass out of the total 100% by mass of the photopolymerization initiator (D) and the ultraviolet absorber (L).

[Antioxidant (M)]
The photosensitive coloring composition of the present invention can contain an antioxidant (M). The antioxidant (M) prevents the photopolymerization initiator (D) and thermosetting compound (I) in the photosensitive coloring composition from oxidizing and yellowing due to heat curing or the thermal process during ITO annealing. . In particular, when the concentration of the black colorant (A) in the photosensitive coloring composition is high, the content of the polymerizable compound (C) is relatively reduced, so it is necessary to increase the amount of the photopolymerization initiator (D) or If the compound is mixed, the cured film tends to yellow. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented. The antioxidant (M) is preferably a compound that does not contain a halogen atom.

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

The hindered phenolic antioxidant is, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H ,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2- t-butyl-5-methylphenol), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis [3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8 , 10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3 ,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2' -Methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis (3,5-di-t-butyl-4-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-hexanedi-rubis[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, 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), 2,4-dimethyl-6-(1-methyl-cyclohexyl)-phenol, and the like.

Commercially available products include, for example, Adeka Stab AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA, and KEMINOX101, 179, 76, 9425 manufactured by Chemipro. , IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565 manufactured by BASF Japan, Syanox CY-1790, CY-2777 manufactured by Sun Chemical, etc. Can be mentioned.

Examples of hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6 -tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6 -tetramethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate , 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine , poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl) ) imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3, Ester of 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, bis(2,2,6,6-tetramethyl-1-(octyloxy) decanedioate) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyriperidyl)[[3,5-bis(1, 1dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate methyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, poly[[6-morpholino-s-triazine-2,4 -diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2, 2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid ester, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1
, 6-hexamethylene diamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propion Amides and the like can be mentioned.

Commercially available products include, for example, ADEKA STAB LA-52, LA-57, LA-63P, LA-68, LA-72, LA-77Y, LA-77G, LA-81, LA-82, LA-87. , LA-402F, LA-502XP, KAMISTAB29, 62, 77, 94 manufactured by Chemipro Kasei Co., Ltd., Tinuvin111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan Co., Ltd., Siasorb UV-3346 manufactured by Sun Chemical Co., Ltd. , UV-3529, UV-3853, etc.

Examples of phosphorus-based antioxidants include di(2,6-di-t-butyl-4-methylphenyl)pentaerythritol diphosphite, distearylpentaerythritol diphosphite, and 2,2'-methylenebis(4,6 -di-t-butylphenyl)2-ethylhexylphosphite, tris(2,4-di-t-butylphenyl)phosphite, tris(nonylphenyl)phosphite, tetra(C12-C15 alkyl)-4,4' -Isopropylidene diphenyl diphosphite, diphenylmono(2-ethylhexyl) phosphite, diphenylisodecyl phosphite, tris(isodecyl) phosphite, triphenyl phosphite, tetrakis(2,4-di-t-butylphenyl)- 4,4-biphenyldiphosphonite, tris(tridecyl)phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi(tridecyl)phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4 '-Isopropylidene diphenol alkyl phosphite, trisnonylphenyl phosphite, trisdinonylphenyl phosphite, tris(biphenyl) phosphite, di(2,4-di-t-butylphenyl)pentaerythritol diphosphite, di (nonylphenyl) pentaerythritol diphosphite, phenylbisphenol A pentaerythritol diphosphite, tetratridecyl 4,4'-butylidenebis(3-methyl-6-t-butylphenol) diphosphite, hexatridecyl 1,1,3- Tris(2-methyl-4-hydroxy-5-t-butylphenyl)butane triphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodium bis(4-t-butylphenyl) phosphite phyto, sodium-2,2-methylene-bis(4,6-di-t-butylphenyl)-phosphite, 1,3-bis(diphenoxyphosphonyloxy)-benzene, ethylbis(2,4-phosphite) -di-t-butyl-6-methylphenyl) and the like.

Commercially available products include, for example, ADEKA STAB PEP-36, PEP-8, HP-10, 2112, 1178, 1500, C, 135A, 3010, TPP manufactured by ADEKA, IRGAFOS168 manufactured by BASF Japan, and HostanoxP manufactured by Clariant Chemicals. - EPQ etc.

Sulfur-based antioxidants include, for example, 2,2-bis{[3-(dodecylthio)-1-oxopropoxy]methyl}propane-1,3-diylbis[3-(dodecylthio)propionate], 3,3'- Ditridecyl thiobispropionate, 2,2-thio-diethylenebis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate], 2,4-bis[(octylthio)methyl]-o- Examples include cresol, 2,4-bis[(laurylthio)methyl]-o-cresol, and the like.

Examples of commercially available products include ADEKA STAB AO-412S and AO-503 manufactured by ADEKA, and KEMINOXPLS manufactured by ChemiPro Kasei.

The antioxidant (M) can be used alone or in combination of two or more.

The content of the antioxidant (M) is preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. Containing an appropriate amount improves transmittance, spectral characteristics, and sensitivity.

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

Examples of silicone surfactants include linear polymers comprising siloxane bonds and modified siloxane polymers having organic groups introduced into side chains or terminals.

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, manufactured by BYK Chemie. 378, 3455, UV3510, 3570, FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Dow Corning Toray, X-22-4952, X-22-4272, X- manufactured by Shin-Etsu Chemical Co., Ltd. 22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

Examples of the fluorosurfactant include a surfactant or a leveling agent having a fluorocarbon chain.

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

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristele ether, polyoxyethylene octyl Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylene distyrenated phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monooleate, sorbitan triolate, sorbitan sesquiolate, polyoxyethylene sorbitan mono Laurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan triisostearate, polyoxytetraoleate Ethylene sorbitol, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monooleate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl Examples include alkanolamide and alkylimidazoline.

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 manufactured by Kao Corporation. , 705, 707, 709, 1108, 1118S-70, 1135S-70, 1150S-60, 2020G-HA, 2025G, LS-106, LS-110, LS-114, MS-110, A-60, A-90 , B-66, PP-290, Latemur PD-420, PD-430, PD-430S, PD-450, Rheodor 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), Amito 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, (meth)acrylic acid-based (co)polymer Polyflo-No. manufactured by Kyoeisha Chemical Co., Ltd. 75, No. 90, No. 95 etc. are mentioned.

Examples of the cationic surfactant include alkyl amine salts, alkyl quaternary ammonium salts such as lauryltrimethylammonium chloride, stearyltrimethylammonium chloride, and cetyltrimethylammonium chloride, and ethylene oxide adducts thereof.

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

Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenyl ether disulfonates, and lauryl sulfate monoethanol. Examples include amine, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, and polyoxyethylene alkyl ether phosphate.

Commercially available products include, for example, Ftergent 100 and 150 manufactured by Neos, ADEKA HOPE YES-25, ADEKA COL TS-230E, PS-440E, and EC-8600 manufactured by ADEKA.

Examples of the amphoteric surfactant include alkyl betaines such as lauric acid amidopropyl betaine, lauryl betaine, cocamidopropyl betaine, stearyl betaine, and alkyldimethylaminoacetic acid betaine, and alkyl amine oxides such as lauryl dimethylamine oxide.

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

The leveling agent (N) can be used alone or in combination of two or more types.

The content of the leveling agent (N) is preferably 0.001 to 2.0% by weight, more preferably 0.005 to 1.0% by weight based on 100% by weight of nonvolatile content of the photosensitive coloring composition. When contained in an appropriate amount, the balance between coating properties and adhesion of the photosensitive coloring composition is further improved.

[Storage stabilizer (O)]
The photosensitive coloring composition of the present invention can contain a storage stabilizer (O). This stabilizes the viscosity of the photosensitive coloring composition over time. Storage stabilizers (O) include, for example, quaternary ammonium chlorides such as benzyl trimethyl chloride and diethyl hydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl. Examples include organic phosphines and phosphites.

The content of the storage stabilizer (O) is preferably 0.1 to 10 parts by weight based on 100 parts by weight of the black colorant (A).

[Adhesion improver (P)]
The photosensitive coloring composition of the present invention can contain an adhesion improver (P). This improves the adhesion between the cured film and the base material. Further, it becomes easier to form a narrow pattern using photolithography.

Examples of the adhesion improver (P) include silane coupling agents. Examples of the silane coupling agent include vinyl silanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, (Meth)acrylic silanes such as 3-methacryloxypropyltriethoxysilane and 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxysilanes, N-2-(aminoethyl)-3-aminopropyl Methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3- Aminosilanes such as hydrochloride of dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyl Mercapto compounds such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryl compounds such as p-styryltrimethoxysilane, ureido compounds such as 3-ureidopropyltriethoxysilane, bis(triethoxysilylpropyl)tetrasulfide, etc. Examples include silane coupling agents such as sulfides and isocyanates such as 3-isocyanatepropyltriethoxysilane.

The adhesion improver (P) can be used alone or in combination of two or more types.

The content of the adhesion improver (P) is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, based on 100 parts by weight of the black colorant (A).

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

The organic solvent (Q) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol. Diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone , ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methoxy Butyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N -Methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, Isophorone, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene Glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether Acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether, dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol Monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene Glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate , propyl acetate, dibasic acid esters, and the like. Among these, from the viewpoint of pigment dispersibility and alkali-soluble resin solubility, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, etc. Alcohols such as glycol acetates, benzyl alcohol and diacetone alcohol, and ketones such as cyclohexanone are preferred.

The organic solvent (Q) can be used alone or in combination of two or more.

[Method for producing photosensitive coloring composition]
The photosensitive coloring composition of the present invention can be produced by adding, for example, a black colorant (A), a dispersion resin (B), a dye derivative (F), an organic solvent (Q), etc., and carrying out a dispersion treatment to form a dispersion. Manufacture. Thereafter, the polymerizable compound (C), the photopolymerization initiator (D), the binder resin (E), and the like are added to the dispersion and mixed. Note that the timing of blending each material is arbitrary. Moreover, the dispersion step can also be performed multiple times.

Examples of the dispersing machine that performs 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.

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. When the particle size is appropriate, it is easy to obtain a photosensitive coloring composition with high dispersion stability.

The average dispersed particle size (secondary particle size) can be measured using, for example, Microtrack UPA-EX150 manufactured by Nikkiso Co., Ltd., which employs a dynamic light scattering method (FFT power spectrum method). D. The particle shape is non-spherical, and the D50 particle diameter is the average diameter. It is preferable to use the organic solvent used for dispersion as the diluting solvent for measurement, and to measure the sample treated with ultrasonic waves immediately after sample preparation, because results with less variation can be easily obtained.

The photosensitive coloring composition is prepared by centrifugation, filtration using a sintered filter or a membrane filter, etc. to obtain coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and It is preferable to remove mixed dust. 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.

<Cured film>
The cured film of the present invention is obtained by curing a film formed using the photosensitive coloring composition of the present invention by a treatment such as exposure. The cured film may be a patterned cured film.

[Method for manufacturing cured film]
The method for producing the cured film is not particularly limited, and includes, for example, step (1) of applying a photosensitive coloring composition onto a substrate to form a layer (film) of the composition, and applying a pattern to the layer through a mask. It can be produced by performing a step (2) of exposing the unexposed portion to light, a step (3) of developing the unexposed portion with alkali to form a patterned cured film, and a step (4) of heating the pattern (post-baking).

The method for manufacturing the cured film will be described in detail below.
(Step (1))
In the step (1) of forming a layer of the composition, the photosensitive coloring composition is applied onto the substrate by a method such as spin coating, roll coating, slit coating, cast coating, or inkjet coating, Dry (prebake) at a temperature of 50 to 120° C. for 10 to 120 seconds using an oven, hot plate, etc. as necessary.
Examples of the substrate include a glass substrate, a silicon substrate, and the like. For example, an image sensor such as a CCD or CMOS may be formed on the surface of the silicon substrate. Further, an undercoat layer may be provided on the substrate, if necessary, in order to improve adhesion between the upper layer and the layer, prevent diffusion of substances, and flatten the surface of the substrate.
The thickness of the layer after drying is preferably 0.05 to 10.0 μm, more preferably 0.3 to 5 μm.

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

(Step (3))
The cured film obtained in step (2) is subjected to an alkali development treatment, whereby the unexposed portions of the composition layer are eluted into the alkaline aqueous solution, leaving only the cured portions to form a patterned cured film.
Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, Examples include alkaline compounds such as pyrrole, piperidine, and 1,8-diazabicyclo-[5.4.0]-7-undecene.
The concentration of the developer is preferably 0.001 to 10% by weight, more preferably 0.01 to 1% by weight.
The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, pattern roughness and peeling can be suppressed and the residual film rate after development can be improved.

Examples of the developing method include a dip method, a spray method, and a paddle method. The developing temperature is preferably 15 to 40°C. Note that after alkaline development, it is preferable to wash with pure water.

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

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

A method for measuring the thickness of the cured film is shown below.

(Measurement of film thickness)
The photosensitive coloring composition of the present invention was applied onto a glass substrate by a spin coating method so that the film thickness after drying was 2.0 μm, dried on a hot plate at 70°C for 1 minute, and then using an ultra-high pressure mercury lamp. , 250 mJ/cm ² . After that, this substrate was heated to 0.2% by mass at 23°C.
After spray development using an aqueous solution of sodium carbonate, the film was washed with ion-exchanged water, air-dried, and heated in a clean oven at 230° C. for 30 minutes (post-baking) to obtain a cured film.
The obtained cured film was measured at five arbitrary points using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.), and the average value was taken as the film thickness.
Note that the above-mentioned film thickness of 2.0 μm includes the range of error allowed in the technical field to which the present invention belongs. Specifically, it means that the film thickness is in the range of 2.0 μm±0.2 μm.

(Measurement of optical density)
The thickness of the cured film was measured at five arbitrary points using a Macbeth densitometer (Gretag Macbeth D200-II), and the average value was taken as the optical density.

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

<Color filter>
The cured film of the present invention can be used for color filters. Although the form used for the color filter is not particularly limited, it is preferable to use it as a black matrix.
The black matrix is a black edge provided at the periphery of an image display device such as a solid-state image sensor or a liquid crystal display device, or a grid-like and/or stripe-like black part between red, blue, and green pixels, Examples include dotted and/or linear black patterns for TFT light shielding.

The color filter can be manufactured, for example, by the following method.
First, a patterned black matrix is formed on a substrate in the same manner as the above-mentioned cured film. Thereafter, a color filter can be manufactured by sequentially forming coating films of red, green, and blue photosensitive coloring compositions on the substrate provided with the black matrix.
Examples of the substrate include a transparent substrate and a reflective substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective base material include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

<Image display device>
The cured film of the present invention can be used for image display devices. The form used in the image display device is not particularly limited, but may include a form including a color filter having the above-mentioned black matrix.

An example of an image display device of the present invention will be described.
The image display device includes the color filter of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED, but in the present invention, it is preferable to use a white LED because the red reproduction area is expanded. FIG. 1 is a schematic cross-sectional view showing an example of the configuration of an image display device equipped with 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 that are spaced apart and facing each other, and a liquid crystal LC is sealed between them.

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. Furthermore, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

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

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

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

The liquid crystal LC is TN (Twisted Nematic), STN (Super Twisted Nematic), IPS (In-Plane Switching), VA (Vertical Alignment), OCB (Optically Compensated).
The orientation is determined according to the drive mode such as birefringence. First transparent substrate 1
A TFT (thin film transistor) array 12 is formed on the inner surface of the substrate 1, and a transparent electrode layer 13 made of ITO, for example, is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13. Furthermore, a polarizing plate 15 is formed on the outer surface of the transparent substrate 11.

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

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

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

White LED light sources include those in which a fluorescent filter is formed on the surface of a blue LED, and those in which a blue LED resin package contains a phosphor. λ3), has a wavelength (λ4) at which the emission intensity is maximum within the range of 530 nm to 580 nm, has a wavelength (λ5) at which the emission intensity is maximum within the range from 600 nm to 650 nm, and has a wavelength The ratio (I4/I3) of the emission intensity I3 at wavelength λ3 and the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio (I5/I3) of the emission intensity I3 at wavelength λ3 and the emission intensity I5 at wavelength λ5 is ) is 0.1 or more and 1.3 or less, or a white LED light source (LED1) that has a wavelength (λ1) with maximum emission intensity in the range of 430nm to 485nm and in the range of 530nm to 580nm. spectral characteristics having a second peak wavelength of emission intensity (λ2) within the range, and a ratio (I2/I1) of emission intensity I1 at wavelength λ1 to emission intensity I2 at wavelength λ2 of 0.2 or more and 0.7 or less. It is preferable to use a white LED light source (LED2).

Examples of the LED 1 include NSSW306D-HG-V1 (manufactured by Nichia Chemicals) and NSSW304D-HG-V1 (manufactured by Nichia Chemicals).

Examples of the LED 2 include NSSW440 (manufactured by Nichia Chemicals) and NSSW304D (manufactured by Nichia Chemicals).

<Solid-state image sensor>
The cured film of the present invention can be used for solid-state imaging devices. The form used for the solid-state image sensor is not particularly limited, but for example, a plurality of photos forming the light receiving area of the solid-state image sensor (such as a CCD image sensor, a CMOS image sensor, or an organic CMOS image sensor) are placed on a substrate. Examples include a configuration having a light receiving element made of a diode, polysilicon, etc., and having the cured film of the present invention on the side where the light receiving element is formed or on the opposite side to the forming surface. FIG. 2 is a schematic cross-sectional view showing a configuration example of a solid-state imaging device including a cured film of the present invention.

As shown in FIG. 2, the solid-state imaging device 200 includes a rectangular solid-state imaging device 201 and a transparent cover glass 203 that is held above the solid-state imaging device 201 and seals the solid-state imaging device 201. There is. Furthermore, a lens layer 211 is provided on top of the cover glass 203 with a spacer 104 interposed therebetween. 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 is diffused, which weakens the light condensing effect of the lens material 212, reducing the amount of light that reaches the imaging unit 202. Further, noise is also generated due to stray light. Therefore, the peripheral region of this lens layer 211 is provided with a cured film (light shielding) 214 of the present invention to shield it from light.

The solid-state imaging device 201 photoelectrically converts an optical image formed by the imaging section 202 serving as its light-receiving surface, and outputs it as an image signal. This solid-state image sensor 201 includes a laminated substrate 205 in which two substrates are laminated. The laminated board 205 consists of a rectangular chip board 206 and a circuit board 207 of the same size, and the circuit board 207 is laminated on the back surface of the chip board 206.

An imaging section 202 is provided at the center of the surface of the chip substrate 206. Furthermore, when stray light enters the peripheral area of the imaging unit 202, dark current (noise) is generated from the circuits in this peripheral area, so this peripheral area is provided with the cured film (light shielding) 215 of the present invention to shield it from light. has been done.

A plurality of electrode pads 208 are provided on the edge of the surface of the chip substrate 206. The electrode pad 208 is electrically connected to the imaging section 202 via a signal line (not shown) provided on the surface of the chip substrate 206.

External connection terminals 209 are provided on the back surface of the circuit board 207 at positions substantially below each electrode pad 208 . Each external connection terminal 209 is connected to an electrode pad 208 via a through electrode 210 that vertically penetrates the laminated substrate 205. In addition, each external connection terminal 209 is connected to a control circuit that controls driving of the solid-state image sensor 201, an image processing circuit that performs image processing on an image signal output from the solid-state image sensor 201, etc. via wiring (not shown). It is connected.

<Infrared sensor>
The cured film of the present invention can be used for infrared sensors. 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 image sensor 310.

The imaging area provided on the solid-state imaging device 310 is configured by combining an infrared absorption filter 311 and a color filter 312.
The infrared absorption filter 311 transmits light in the visible region (for example, light with a wavelength of 400 to 700 nm) and blocks light in the infrared region (for example, light with a wavelength of 800 to 1300 nm).
The color filter 312 is a color filter in which pixels that transmit and absorb light of a specific wavelength in the visible light region are formed, and for example, red (R), green (G), and blue (B) pixels are formed. A color filter or the like is used.

A resin film 314 is arranged between the infrared transmission filter 313 and the solid-state image sensor 310 and is capable of transmitting light having a wavelength that has passed through the infrared transmission filter 313.
The infrared transmission filter 313 is a filter that has visible light shielding properties and transmits infrared rays of a specific wavelength, and the cured film of the present invention containing the above-mentioned near-infrared absorber (G) can be used. For example, 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.

A microlens 315 is arranged on the incident light side of the color filter 312 and the infrared transmission filter 313. A flattening film 316 is formed to cover the microlens 315.

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

The cured film of the present invention can be used as a light-shielding film on the edge and/or side surface of the infrared absorption filter 311, and can also be used on the inner wall of an infrared sensor to prevent internal reflection and/or unnecessary light to the light receiving part. can be prevented from entering and improve sensitivity.

According to this infrared sensor, image information can be captured at the same time, so motion sensing and the like that recognize the target whose movement is to be detected are possible. Further, since distance information can be acquired using this infrared sensor, it is also possible to take images including 3D information. Furthermore, this infrared sensor can also be used as a biometric sensor.

Furthermore, 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, the TFT as a switching element may malfunction due to light incident on the TFT, and colored spacers are used to prevent this. The colored spacers can be formed in the same manner as the black matrix described above, except for using a mask for colored spacers.

Further, the cured film of the present invention can also be used for applications such as micro LEDs (Light Emitting Diodes) and micro OLEDs (Organic Light Emitting Diodes). Although not particularly limited, it is suitably used for optical filters and optical films used in micro LEDs and micro OLEDs, as well as members that provide light shielding and antireflection properties.
Examples of micro LEDs and micro OLEDs include those described in Japanese Translation of PCT Publication No. 2015-500562 and Japanese Translation of PCT Publication No. 2014-533890.

Moreover, the cured film of the present invention can also be used for applications such as quantum dot displays. Although not particularly limited, it is suitably used for optical filters and optical films used in quantum dot displays, as well as members that provide light-shielding and antireflection properties.

Hereinafter, the present invention will be explained in more detail with reference to Examples. However, the present invention is not limited to these. Note that "part" means "part by mass" and "%" means "% by mass."
Furthermore, in the present invention, the nonvolatile content or nonvolatile content concentration refers to the mass remaining after standing in an oven at 280°C for 30 minutes.

Prior to Examples, each measurement method will be explained.

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

(Average molecular weight of binder resin and dispersion resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the binder resin and the dispersion resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. HLC-8220GPC (manufactured by Tosoh Corporation) was used as the equipment, two separation columns were connected in series, and the packing material for both was "TSK-GEL SUPER HZM-N" connected in two series, and the oven temperature was 40℃. The measurement was performed at a flow rate of 0.35 ml/min using a tetrahydrofuran (THF) solution as an eluent. The sample was dissolved in a solvent consisting of 1 wt % of the above eluent, and 20 microliters was injected. The molecular weight is a polystyrene equivalent value.

(Acid value of binder resin and dispersion resin)
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of binder resin and dispersion resin solution, stir to dissolve uniformly, and use an automatic titrator (COM- 555 (manufactured by Hiranuma Sangyo Co., Ltd.) to measure the acid value (mgKOH/g). Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the nonvolatile content concentration of the resin solution.

(Amine value of dispersion resin)
The amine value of the dispersion resin is the value obtained by converting the total amine value (mgKOH/g) measured in accordance with the method of ASTM D 2074 into nonvolatile content.

<Manufacture of organic pigments>
(Fine blue organic pigment)
C. I. 100 parts of Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyo Color Co., Ltd.), 800 parts of crushed sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and heated at 70°C for 12 hours. Kneaded. This mixture was poured into 3,000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, and after repeated filtration and water washing to remove sodium chloride and diethylene glycol, the mixture was heated to about 70°C A fine blue organic pigment was obtained by drying the mixture for one day and pulverizing it.

(Fine yellow organic pigment)
C. I. 100 parts of Pigment Yellow 139 ("Novoperm Yellow P-M3R" manufactured by Clariant), 800 parts of crushed sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 12 hours. . This mixture was poured into 3000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, the mixture was kept at 80°C overnight. A fine yellow organic pigment was obtained by drying and pulverizing.

(Fine purple organic pigment)
C. I. 100 parts of Pigment Violet 23 (LIONOGEN VIOLET FG-6140 manufactured by Toyo Color Co., Ltd.), 800 parts of crushed sodium chloride, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 12 hours. did. This mixture was poured into 3000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, the mixture was kept at 80°C overnight. A finely divided purple organic pigment was obtained by drying and pulverizing.

<Manufacture of dispersed resin (B)>
(Dispersion resin (B1-1) solution having acidic groups)
A reaction vessel equipped with a gas inlet tube, temperature, condenser, and stirrer was charged with 10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate, and 50 parts of PGMAc, and the mixture was purged with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50°C, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90° C., and a reaction was carried out for 7 hours while adding a solution of 0.1 part of 2,2'-azobisisobutyronitrile to 90 parts of propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc). It was confirmed by non-volatile content measurement that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 part of 1,8-diazabicyclo-[5.4.0]-7-undecene as a catalyst were added and reacted at 100°C for 7 hours. . After confirming that 98% or more of the acid anhydride was half-esterified by measuring the acid value, the reaction was terminated, and the mixture was diluted with PGMAc so that the non-volatile content was 30% by measuring the non-volatile content, and the acid value was 70 mgKOH/g. A dispersion resin (B1-1) solution having an acidic group and a weight average molecular weight of 8,500 was obtained.

(Dispersion resin (B1-1-2) solution having acidic groups)
108 parts of 1-thioglycerol, 174 parts of pyromellitic anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were placed in a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, and the mixture was heated with nitrogen gas. After the substitution, the mixture was reacted at 120° C. for 5 hours (first step). Acid value measurement confirmed that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step in terms of nonvolatile content, 200 parts of 2-hydroxypropyl methacrylate, 200 parts of ethyl acrylate, 150 parts of t-butyl acrylate, 200 parts of 2-methoxyethyl acrylate, and 200 parts of methyl acrylate. 1 part, 50 parts of methacrylic acid, and 663 parts of PGMAc were charged, the inside of the reaction vessel was heated to 80°C, 1.2 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) was added, and the mixture was reacted for 12 hours. (Second step). It was confirmed by non-volatile content measurement that 95% had reacted. Finally, 500 parts of a 50% PGMAc solution of the compound obtained in the second step, 27.0 parts of 2-methacryloyloxyethyl isocyanate (MOI), and 0.1 part of hydroquinone were charged, and 2270 cm based on the isocyanate group was measured by IR. The reaction was continued until the disappearance of ^{the -1} peak was confirmed (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 (B1-1-2) solution having acidic groups with a nonvolatile content of 30%. The obtained dispersion resin (B1-1-2) having acidic groups had an acid value of 68 mgKOH/g, an unsaturated double bond equivalent of 1,593, and a weight average molecular weight of 13,000.

(Other dispersion resin (B2-1) solution)
40 parts of methyl methacrylate, 10 parts of n-butyl methacrylate, and 13.2 parts of tetramethylethylenediamine as a catalyst were charged into a reaction apparatus equipped with a gas introduction pipe, a condenser, a stirring blade, and a thermometer, and the mixture was heated at 50°C while flowing nitrogen. The mixture was stirred for 1 hour, and the atmosphere in the system was replaced 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, and the temperature was raised to 110°C under a nitrogen stream to form the first block (B block). Polymerization started. After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content. Next, 50 parts of PGMAc, 40 parts of dimethylaminoethyl methacrylate as a second block (A block) monomer, and 10 parts of methacryloyloxyethylbenzyldimethylammonium chloride were added to this reactor, and the temperature was maintained at 110°C under a nitrogen atmosphere. The reaction was continued with stirring. Two hours after the addition, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate of the second block (block A) was 98% or more in terms of nonvolatile content, and the reaction solution was heated to room temperature. Polymerization was stopped by cooling. As a result of GPC measurement, the mass average molecular weight of the polymer was 20,000, the molecular weight distribution Mw/Mn was 1.4, and the reaction conversion rate was 98.5%. In this way, a basic dispersion resin (B2-1) having an amine value per nonvolatile content of 169.8 mgKOH/g was obtained. After cooling to room temperature, about 2 g was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content. PGMAc was added so that the nonvolatile content was 30% by mass, and other dispersed resins having basic groups were added. (B2-1) A solution was prepared.

<Production of polymerizable compound (C)>
(Polymerizable compound (C1-1) solution having urethane bond)
400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N,N-dimethylbenzylamine were charged into a 5-necked flask equipped with a stirrer, a reflux condenser, a nitrogen inlet tube, a thermometer, and a dropping tube. The temperature was raised to 0.degree. C., and a mixture of 64 parts of hexamethylene diisocyanate and 64 parts of PGMAc was added dropwise from a dropping tube over 2 hours. After dropping, the mixture was reacted for 8 hours at a temperature of 50 to 70°C, and the disappearance of isocyanate absorption at 2180 cm- ¹ was confirmed by IR. PGMAc was added so that the nonvolatile content was 50% by mass to obtain a solution of a polymerizable compound (C1-1) having a urethane bond having 10 polymerizable unsaturated groups.

(Polymerizable compound (C1-2) solution having urethane bond)
Into a 5-necked flask equipped with a stirrer, reflux condenser, nitrogen inlet tube, thermometer, and dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N,N-dimethylbenzylamine were charged. The temperature was raised to .degree. C., and a mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from a dropping tube over 2 hours. After dropping, the mixture was allowed to react at a temperature of 50 to 70°C for 8 hours, and the disappearance of isocyanate absorption at 2180 cm- ¹ was confirmed by IR. Then, 35 parts of mercaptoacetic acid and 0.6 parts of 4-methoxyphenol were charged, and the mixture was reacted at a temperature of 50 to 60°C for 6 hours. The nonvolatile content was adjusted to 50% by mass to obtain a solution of a polymerizable compound (C1-2) having a urethane bond with an average number of polymerizable unsaturated groups of 9.

<Production of binder resin (E)>
(Binder resin (E-1) solution)
100 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, the temperature was raised to 80°C, the inside of the reaction vessel was replaced with nitrogen, and then added dropwise. From the tube, 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 ("Aronix M110" manufactured by Toagosei Co., Ltd.) A mixture of 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 40%. A binder resin (E-1) solution was prepared. The weight average molecular weight (Mw) was 26,000.

(Binder resin (E-2) solution)
100 parts of cyclohexanone was placed in a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device. 100 parts of cyclohexanone was then heated to 80°C, the inside of the reaction vessel was replaced with nitrogen, and then added dropwise. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene 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 of isobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain a resin solution. Next, the entire amount of the obtained resin solution was stirred while stopping nitrogen gas and injecting dry air for 1 hour, and then cooled to room temperature, and then added 2-methacryloyloxyethyl isocyanate (Karens MOI, manufactured by Showa Denko). A mixture of 6.5 parts of dibutyltin laurate, 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 40%. A binder resin (E-2) solution was prepared. The weight average molecular weight (Mw) was 18,000.

(Binder resin (E-3) solution)
200 parts of cyclohexanone was charged into a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, and the temperature was raised to 80°C. After replacing the inside of the flask with nitrogen, 18 parts of milphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile. part of the mixture was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, and then a solution of 1.0 part of azobisisobutyronitrile dissolved in 20 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container was replaced with air, and 9.3 parts of acrylic acid (equimolar amount to the glycidyl group), 0.5 part of trisdimethylaminophenol, and 0.1 part of hydroquinone were put into the container, and 120 The reaction was continued at ℃ for 6 hours, and the reaction was terminated when the non-volatile acid value reached 0.5 to obtain a solution of acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl groups) and 0.5 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content. PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 40% by mass. A binder resin (E-3) solution was prepared. The weight average molecular weight (Mw) was 19,000.

(Binder resin (E-4) solution)
A separable flask equipped with a cooling tube was prepared as a reaction tank, and on the other hand, as a monomer dropping tank, 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, and methacrylic acid were prepared. Prepare a well-stirred mixture of 120 parts of methyl, 4 parts of t-butyl peroxy 2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation), and 40 parts of PGMAc, and use it as a chain transfer agent dropping tank to add n-dodecanethiol. A mixture of 8 parts of PGMAc and 32 parts of PGMAc was prepared by thoroughly stirring and mixing.
After charging 200 parts of PGMAc into a reaction tank and replacing the atmosphere with nitrogen, the reaction tank was heated in an oil bath while stirring to raise the temperature of the reaction tank to 90°C. After the temperature of the reaction tank stabilized at 90° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. Each dropwise addition took 135 minutes while maintaining the temperature at 90°C. 60 minutes after the dropwise addition was completed, the temperature was started to rise to 110° C. in the reaction tank. After maintaining the temperature at 110°C for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen = 5/95 (volume ratio) was started. 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 placed in a reaction tank, and the mixture was allowed to react at 110°C for 12 hours. Ta. After that, 150 parts of PGMAc was added and cooled to room temperature, and about 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content, and the nonvolatile content was 40% by mass in the resin solution synthesized earlier. PGMAc was added to obtain a binder resin (E-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per nonvolatile content was 2 mgKOH/g.

(Binder resin (E-5) solution)
150 parts of PGMAc was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube. After changing the atmosphere inside the flask from air to nitrogen, the temperature was raised to 100°C, and benzyl methacrylate was added. 70.5 parts (0.40 mol) of glycidyl methacrylate, 71.1 parts (0.50 mol) of glycidyl methacrylate, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 164 parts of PGMAc. A solution containing 3.6 parts of butyronitrile was added dropwise from the dropping funnel to the flask over 2 hours, and the mixture was further stirred at 100°C for 5 hours. Next, the atmosphere in the flask was changed from nitrogen to air, and 43.0 parts of methacrylic acid [0.5 mol, (equimolar amount to the glycidyl group of glycidyl methacrylate used in this reaction)] and 0 parts of trisdimethylaminomethylphenol were added. .9 parts and 0.145 parts of hydroquinone were put into the flask, and the reaction was continued at 110° C. for 6 hours, and the reaction was terminated when the nonvolatile acid value reached 1 mgKOH/g. Next, 60.9 parts (0.40 mol) of tetrahydrophthalic anhydride and 0.8 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain a resin solution with an acid value of 80 mgKOH/g. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180° C. for 20 minutes, and the nonvolatile content was measured. Next, PGMAc was added so that the nonvolatile content was 40% by mass to prepare a binder resin (E-5) solution. The weight average molecular weight (Mw) was 12,000.

(Binder resin (E-6) solution)
150 parts of PGMAc was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube. After changing the atmosphere inside the flask from air to nitrogen, the temperature was raised to 100°C, and benzyl methacrylate was added. 70.5 parts (0.40 mol), 43.0 parts (0.5 mol) of methacrylic acid, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and PGM
A solution of 3.6 parts of azobisisobutyronitrile added to a mixture of 136 parts of Ac was added dropwise to the flask from the dropping funnel over 2 hours, and the mixture was further stirred at 100°C for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate [0.25 mol, (50 mol % based on the carboxyl group of methacrylic acid used in this reaction)] and 0 parts of trisdimethylaminomethylphenol were added. .9 parts and 0.145 parts of hydroquinone were put into the flask, and the reaction was continued at 110° C. for 6 hours to obtain a resin solution with an acid value of 79 mgKOH/g. After cooling to room temperature, about 2 parts of the resin solution was sampled, heated and dried at 180° C. for 20 minutes, and the nonvolatile content was measured. Next, PGMAc was added so that the nonvolatile content was 40% by mass to prepare a binder resin (E-6) solution. The weight average molecular weight (Mw) was 13,000.

<Production of near-infrared absorber (G)>
(Near infrared absorber (G-1))
40.0 parts of 1,8-diaminonaphthalene, 32.2 parts of 3,5-dimethylcyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate were mixed with 400 parts of toluene, and the mixture was mixed in a nitrogen gas atmosphere. The mixture was heated and stirred 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 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, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was placed in a nitrogen gas atmosphere. The mixture was heated and stirred for 8 hours under reflux. 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 200 parts of hexane was added to the resulting reaction mixture while stirring. After filtering the obtained black brown precipitate, it was washed sequentially with hexane, ethanol and acetone, and dried under reduced pressure to obtain a near-infrared absorber (G-1) represented by the following chemical formula (9). Ta. 50 parts of the obtained near-infrared absorber (G-1), 500 parts of sodium chloride, and 60 parts of diethylene glycol were placed in a stainless steel gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 12 hours. Next, the kneaded mixture was poured into warm water and stirred for 1 hour while heating to about 80°C to form a slurry. After filtering and washing with water to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight and pulverized. By doing so, a finely divided near-infrared absorber (G-1) was obtained.

Chemical formula (9)

<Production of dispersion>
(Dispersion 1)
After stirring and mixing the following raw materials so that they were uniform, they were dispersed for 3 hours using an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) using zirconia beads with a diameter of 0.5 mm, and then the pore size was Dispersion 1 was prepared by filtration with a 1.0 μm filter. The organic solvent (Q-1) is PGMAc.
Carbon black (Mitsubishi Chemical #850): 20.0 parts Dispersion resin having acidic group (B1-1) solution: 26.7 parts Pigment derivative (F-1): 1.3 parts Organic solvent (Q-1) ): 52.0 copies

#850 manufactured by Mitsubishi Chemical Corporation is carbon black with an average primary particle diameter of 17 nm and a specific surface area of 220 m ² /g.

Pigment derivative (F-1): structure below

(Dispersion 2 to 5)
Dispersions 2 to 5 were prepared in the same manner as Dispersion 1 except that the raw materials and amounts listed in Table 2 were changed.

Dye derivative (F-2) in Table 2: structure below

<Manufacture of photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition 1)
Mix and stir the following raw materials, filter through a filter with a pore size of 1.0 μm, and prepare photosensitive coloring composition 1.
I got it.
Dispersion 1: 19.00 parts Polymerizable compound having urethane bond (C1-1) Solution: 6.00 parts Other polymerizable compounds (C2-3): 3.00 parts Oxime represented by general formula (1) System photopolymerization initiator (D1-1): 0.40 parts Other photopolymerization initiators (D2-6): 0.10 parts Binder resin (E) solution: 20.00 parts Sensitizer (H): 0. 10 parts Thermosetting compound (I): 1.0 part Thiol chain transfer agent (J): 0.1 part Polymerization inhibitor (K): 0.01 part Ultraviolet absorber (L): 0.1 part Oxidation Inhibitor (M): 0.1 part Leveling agent (N): 1.0 part Organic solvent (Q): 49.09 parts

[Examples 2 to 32, Comparative Examples 1 to 3]
(Photosensitive coloring compositions 2 to 35)
Photosensitive coloring compositions 2 to 35 were produced in the same manner as in Example 1, except that photosensitive coloring composition 1 of Example 1 was changed to the raw materials and amounts listed in Tables 3-1 to 3-3. did.

The raw materials listed in Tables 3-1 to 3-3 are as follows.

[Polymerizable compound (C)]
(Other polymerizable compounds (C2))
C2-1: Aronix M-521 (manufactured by Toagosei Co., Ltd., acrylate with acid group)
C2-2: KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd., lactone-modified acrylate)
C2-3: OGSOL EA-0200 (manufactured by Osaka Gas Chemical Co., Ltd., acrylate with cardo structure)
C2-4: KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)

[Photopolymerization initiator (D)]
(Oxime photopolymerization initiator (D1))
D1-1: Compound of the above chemical formula (3) D1-2: Compound of the above chemical formula (4) D1-3: Compound of the above chemical formula (5) D1-4: Compound of the above chemical formula (6) D1- 5: Compound of the above chemical formula (7) D1-6: Compound of the above chemical formula (8)

(Other photopolymerization initiators (D2))
D2-1: Omnirad 369 (manufactured by IGM Resins, acetophenone photopolymerization initiator)
D2-2: Omnirad 907 (manufactured by IGM Resins, acetophenone photopolymerization initiator)
D2-3: Omnirad TPO (manufactured by IGM Resins, acylphosphine oxide photopolymerization initiator)
D2-4: IRGACURE OXE-04 (manufactured by BASF, oxime-based photopolymerization initiator)
D2-5: ADEKA Arkles NCI-730 (manufactured by ADEKA, oxime-based photopolymerization initiator)
D2-6: TRONLY TR-PBG-3054 (manufactured by Changzhou Strong New Materials Co., Ltd., oxime-based photopolymerization initiator)

[Binder resin (E) solution]
Binder resin (E-1) to (E-6) solutions were mixed in equal amounts to obtain a binder resin (E) solution.

[Sensitizer (H)]
H-1: Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)
H-2: CHEMARK DEABP (manufactured by Chemark Chemical)
As described above, (H-1) and (H-2) were mixed in the same amount to prepare a sensitizer (H).

[Thermosetting compound (I)]
(Epoxy compound (I1)
I1-1: EHPE-3150 (manufactured by Daicel)
I1-2: Denacol EX611 (manufactured by Nagase ChemteX)
I1-3: Triglycidyl isocyanurate and above (I1-1) to (I1-3) were mixed in equal amounts to prepare a thermosetting compound (I).

[Thiol chain transfer agent (J)]
J-1: Trimethylol ethane tris (3-mercaptobutyrate)
J-2: Trimethylolpropane tris (3-mercaptobutyrate)
J-3: Pentaerythritol tetrakis (3-mercaptopropionate)
J-4: Trimethylolpropane tris (3-mercaptopropionate)
J-5: Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate or above, (J-1) to (J-5) are mixed in equal amounts, and mixed with a thiol chain transfer agent (J). did.

[Polymerization inhibitor (K)]
K-1: 4-Methylcatechol K-2: Methylhydroquinone K-3: t-Butylhydroquinone The above (K-1) to (K-3) were mixed in the same amount, and the polymerization inhibitor (K) was added. And so.

[Ultraviolet absorber (L)]
L-1: TINUVIN400 (manufactured by BASF Japan)
L-2: TINUVIN900 (manufactured by BASF Japan)
As described above, (L-1) and (L-2) were mixed in the same amount to prepare an ultraviolet absorber (L).

[Antioxidant (M)]
M-1: Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate M-2: Dioctadecyl 3,3'-thiodipropanoate M-3: Tris[2,4- Di-(t)-butylphenyl]phosphine M-4: Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate M-5: p-octylphenyl salicylate Above, (M-1) to ( M-5) were mixed in the same amount to prepare an antioxidant (M).

[Leveling agent (N)]
N-1: BYK-330 (manufactured by BYK Chemie)
N-2: Megafac F-551 (manufactured by DIC)
A mixed solution in which 1 part each of (N-1) and (N-2) were mixed and dissolved in 98 parts of PGMAc was used as a leveling agent (N).

[Organic solvent (Q)]
Q-1: Propylene glycol monomethyl ether acetate 30 parts Q-2: Cyclohexanone 30 parts Q-3: Ethyl 3-ethoxypropionate 10 parts Q-4: Propylene glycol monomethyl ether 10 parts Q-5: Cyclohexanol acetate 10 parts Q -6: Dipropylene glycol methyl ether acetate 10 parts The above (Q-1) to (Q-6) were mixed in the above mass parts, respectively, to obtain an organic solvent (Q).

<Evaluation of photosensitive coloring composition>
The obtained photosensitive coloring compositions 1 to 35 (Examples 1 to 32, Comparative Examples 1 to 3) were evaluated for optical density, developability, pattern formability, and surface wrinkles by the following methods. The evaluation results are shown in Table 4.

[Optical density (OD value) evaluation]
The obtained photosensitive coloring composition was applied to a glass substrate (Eagle 2000 manufactured by Corning Inc.) measuring 100 mm long x 100 mm wide and 0.7 mm thick by spin coating so that the film thickness after drying was 2.0 μm. After drying on a hot plate at 70° C. for 1 minute, the entire surface was exposed to light at 250 mJ/cm ² using an ultra-high pressure mercury lamp. Thereafter, this substrate was spray developed using 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. (post-baking) to obtain a cured film. The optical density (OD value) of the obtained cured film was measured using a Macbeth densitometer (GretagMacbeth D200-II). The evaluation criteria are as follows, and 2 or more is practical.
3: OD value is 2.0 or more 2: OD value is 1.8 or more but less than 2.0 1: OD value is less than 1.8

[Developability evaluation]
The obtained photosensitive coloring composition was coated onto a glass substrate (Eagle 2000 manufactured by Corning Inc.) measuring 100 mm long x 100 mm wide and 0.7 mm thick using a spin coater so that the dry film thickness was 2.0 μm. , and dried on a hot plate at 70°C for 1 minute. Next, using an ultra-high pressure mercury lamp, the film was exposed to ultraviolet light at an illuminance of 30 mW/cm ² and 250 mJ/cm ² through a photomask with a 100 μm wide stripe pattern. Furthermore, after cooling this substrate to room temperature, spray development was performed using an organic alkaline developer NMD-3 (manufactured by Tokyo Ohka Kogyo Co., Ltd.) at 23°C for two levels of development time (40 seconds and 70 seconds), and ion-exchanged water was used. It was washed and air dried. The obtained substrate was post-baked at 230° C. for 30 minutes in a clean oven to form a striped pattern on the substrate. The pattern was observed with an optical microscope, and the presence or absence of development residue and chipping in unexposed areas was evaluated. The evaluation criteria are as follows, and 2 or more is practical.
3: At a development time of 70 seconds, there was no development residue in the unexposed area, and there was no pattern chipping.
2: At a development time of 70 seconds, development residue or pattern chipping occurred in unexposed areas.
1: At a development time of 40 seconds, development residue or pattern chipping occurred in unexposed areas.

[Pattern formation evaluation (1): Adhesion]
The obtained photosensitive coloring composition was applied to a glass substrate (Eagle 2000 manufactured by Corning Inc.) measuring 100 mm long x 100 mm wide and 0.7 mm thick by spin coating so that the film thickness after drying was 2.0 μm. and dried on a hot plate at 70°C for 1 minute. Next, after cooling this substrate to room temperature, it was exposed to light using a high-pressure mercury lamp at an illuminance of 30 mW/cm ² and 250 mJ/cm ² through a photomask having a stripe pattern with a width of 5 μm. After that, this substrate was 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 adhere. A substrate for performance evaluation was obtained. Spray development was carried out for the shortest time in which a pattern could be formed without any development residue for the film formed with each photosensitive coloring composition, and this was defined as the appropriate development time.
Among the substrates for evaluating pattern formability created by the above method, patterns with widths of 5, 10, 15, 20, and 25 μm were observed with an optical microscope to confirm the minimum line width of the remaining patterns. The evaluation criteria are as follows, and scores of 3 or higher are considered practical.
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.

[Pattern formation evaluation (2): Linearity]
The substrate prepared in pattern formability evaluation (1) was evaluated by measuring the maximum and minimum line widths of the stripe pattern at 10 locations using a Nikon ECLIPSE LV100POL Model optical microscope and calculating the average. Ta. The evaluation criteria are as follows, and 3 or more is 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 The difference 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

[Surface wrinkle evaluation]
The pattern surface of the substrate prepared for adhesion evaluation was observed using an optical microscope ("BX-51" manufactured by Olympus Optical Co., Ltd., magnification: 200 times). The evaluation criteria are as follows, and 3 or more is practical.
5: No wrinkles are observed on the surface of the pattern.
4: Very slight wrinkles are observed on the surface of the pattern.
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.

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 Aligning layer 25 Polarizing plate 30 Backlight unit 31 White LED light source LC Liquid crystal 200 Solid-state imaging device 201 Solid-state imaging device 202 Imaging unit 203 Cover glass 204 Spacer 205 Laminated board 206 Chip board 207 Circuit board 208 Electrode pad 209 External connection terminal 210 Penetrating electrode 211 Lens layer 212 Lens material 213 Support 214 Cured film (light shielding)
215 Cured film (light shielding)
300 Infrared sensor 310 Solid-state image sensor 311 Infrared absorption filter 312 Color filter 313 Infrared transmission filter 314 Resin film 315 Micro lens 316 Flat film

[Examples 2 to 32, Comparative Examples 1 to 3]
(Photosensitive coloring compositions 2 to 35)
Photosensitive coloring compositions 2 to 35 were produced in the same manner as in Example 1, except that photosensitive coloring composition 1 of Example 1 was changed to the raw materials and amounts listed in Tables 3-1 to 3-3. did. Note that Example 1 in this specification is a reference example.

Claims (12)

A photosensitive coloring composition comprising a black colorant (A), a dispersion resin (B), a polymerizable compound (C), and a photopolymerization initiator (D),
A photosensitive coloring composition in which the photopolymerization initiator (D) contains an oxime photopolymerization initiator (D1) represented by the following general formula (1).
General formula (1)


(In general formula (1), R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or Represents 2 to 20 heterocyclic groups.
R ₂ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₃ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₄ represents any monovalent substituent. n represents an integer from 0 to 3. ) The photosensitive coloring composition according to claim 1, wherein the polymerizable compound (C) includes a polymerizable compound (C1) having a urethane bond. The photosensitive coloring composition according to claim 2, wherein the polymerizable compound (C) further contains a polymerizable compound (C2) other than the polymerizable compound (C1) having a urethane bond. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the dispersion resin (B) contains a dispersion resin (B1) having an acidic group. The photosensitive coloring composition according to any one of claims 1 to 4, wherein the black colorant (A) contains carbon black. Any one of claims 1 to 4, wherein the black colorant (A) contains two or more organic pigments selected from the group consisting of a red organic pigment, a yellow organic pigment, a green organic pigment, a blue organic pigment, and a violet organic pigment. The photosensitive coloring composition according to item 1. A cured film that is a cured product of the photosensitive coloring composition according to any one of claims 1 to 6. A light-shielding filter comprising the cured film according to claim 7. A color filter comprising the cured film according to claim 7. An image display device comprising the cured film according to claim 7. A solid-state imaging device comprising the cured film according to claim 7. An infrared sensor comprising the cured film according to claim 7.