JP2022099839A - Photosensitive coloring composition, color filter using the same, image display device, and solid state imaging element - Google Patents

Abstract

To provide a photosensitive coloring composition which has little generation of wrinkles on a pattern surface, suppresses water stains after development, and has excellent pattern formation property (adhesion, shape, and residual film ratio).SOLUTION: A photosensitive coloring composition contains a coloring agent (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D), in which the polymerizable compound (C) contains acid group-containing aromatic urethane (meth)acrylate (C1) and lactone-modified (meth)acrylate (C2).SELECTED DRAWING: None

Description

The present invention relates to a photosensitive coloring composition, a color filter using the same, an image display device, and a solid-state image pickup device.

The color filter is formed by arranging two or more kinds of fine band-shaped filter segments having different hues in parallel (stripe pattern) or intersecting each other on a transparent substrate such as a glass substrate, or the hue. Two or more kinds of fine filter segments having different values are arranged so as to be arranged in order in each of the vertical direction and the horizontal direction. The filter segments have small dimensions of a few microns to a few hundreds of microns and are neatly arranged in a predetermined arrangement for each hue.

Currently, as a method for manufacturing a color filter, a step of applying a photosensitive coloring composition to a transparent substrate such as glass and removing a solvent from the coating film by drying, and a photo of this coating film having a desired pattern shape. A step of irradiating and curing radiation through a mask (hereinafter referred to as exposure), then a step of cleaning and removing the unexposed portion of this coating film (hereinafter referred to as development), and then sufficiently applying a cured film as necessary. A first color filter segment pattern is obtained by a heat treatment (hereinafter referred to as post-baking) step for curing. Then, by performing the same operation as this, a filter segment pattern of another color is formed, and the color filter is completed.

In the above-mentioned developing step, an alkaline developing solution is used as a developing solution to clean and remove the unexposed portion. At that time, there is a problem that the exposed portion is chipped or peeled off and a defect occurs in the pattern shape. Further, when the coating film is exposed to an alkaline developer, there is also a problem that a phenomenon of discoloration of the coating film (hereinafter referred to as water stain) occurs. Therefore, there is a demand for a photosensitive coloring composition that does not cause defective pattern shape and water stain in the developing process. Further, there is also a problem that the film thickness of the coating film changes (hereinafter referred to as the residual film ratio) due to elution or vaporization of unreacted substances or the like during the developing process or the post-baking process.

Further, in recent years, the area per pixel tends to be smaller due to the miniaturization and the increase in the number of pixels of the image display device, and the concentration and the film thickness of the colorant contained in the composition forming the color filter are increased. Etc. are being considered. However, when the concentration and the film thickness of the colorant are increased, there is a problem that wrinkles are generated on the surface of the film during curing.

As an effort to improve water stains, Patent Document 1 discloses a resist composition containing a fluorine-based surfactant having a specific structure. Further, as an effort to improve pattern chipping during development, Patent Document 2 discloses a coloring composition containing a polymerizable compound having an alkylene oxide structure. Further, as an effort to improve the pattern-forming property when a high-concentration colorant is contained, Patent Document 3 discloses a colored photosensitive resin composition containing a polyfunctional thiol compound and an acetophenone compound. Further, as an effort to improve wrinkles on the surface of the film, Patent Document 4 discloses a colored resin composition containing a photopolymerizable monomer having a double bond equivalent of 400 g / mol or less and having a bisphenol skeleton. It is.

Japanese Unexamined Patent Publication No. 2016-102212 Japanese Unexamined Patent Publication No. 2014-142582 Japanese Unexamined Patent Publication No. 2004-83857 Japanese Unexamined Patent Publication No. 2019-183053

However, none of the compositions of Patent Documents 1 to 4 is satisfactory in terms of water stain, adhesion, and surface wrinkles. In addition, the residual film ratio was not considered and was not satisfactory.

It is an object of the present invention to provide a photosensitive coloring composition having less wrinkles on the surface of a pattern, suppressing water stains after development, and having excellent pattern forming properties (adhesion, shape, residual film ratio). And.

The present invention is a photosensitive coloring composition containing a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D).
A photosensitive coloring composition comprising an acid group-containing aromatic urethane (meth) acrylate (C1) and a lactone-modified (meth) acrylate (C2), wherein the polymerizable compound (C) comprises an acid group-containing aromatic urethane (meth) acrylate (C1).
Regarding.

Further, in the present invention, the total content of the acid group-containing aromatic urethane (meth) acrylate (C1) and the lactone-modified (meth) acrylate (C2) is 20 in 100% by mass of the polymerizable compound (C). The present invention relates to the above-mentioned photosensitive coloring composition having a mass% or more.

Further, in the present invention, the polymerizable compound (C) is further selected from the group consisting of an aliphatic urethane (meth) acrylate (C3) and an alicyclic urethane (meth) acrylate (C4). The present invention relates to the above-mentioned photosensitive coloring composition.

Further, the present invention includes the total amount of the acid group-containing aromatic urethane (meth) acrylate (C1), the aliphatic urethane (meth) acrylate (C3) and the alicyclic urethane (meth) acrylate (C4). With respect to the photosensitive coloring composition having a mass ratio of 90:10 to 50:50.

The present invention also relates to the above-mentioned photosensitive coloring composition in which the photopolymerization initiator (D) contains an oxime-based compound (D1).

The present invention also relates to the above-mentioned photosensitive coloring composition, wherein the oxime-based compound (D1) contains an oxime-based compound (D1-2) containing two oxime groups in one molecule.

The present invention further relates to the above-mentioned photosensitive coloring composition containing the sensitizer (E).

The present invention also relates to a substrate and a color filter having a filter segment formed by using the photosensitive coloring composition.

The present invention also relates to an image display device having the above color filter.

The present invention also relates to a solid-state image sensor having the above color filter.

According to the above invention, a photosensitive coloring composition having less wrinkles on the surface of a pattern film, suppressing water stains after development, and having excellent pattern forming properties (adhesion, shape, residual film ratio) can be obtained. Can be provided. The present invention can also provide a color filter, an image display device, and a solid-state image pickup device.

Hereinafter, embodiments for carrying out the photosensitive coloring composition of the present invention will be described in detail. The present invention is not limited to the following embodiments, and can be modified and implemented within a range in which the problem can be solved.

In the present invention, "(meth) acryloyl", "(meth) acrylic", "(meth) acrylic acid", "(meth) acrylate", or "(meth) acrylamide" are referred to as "(meth) acrylamide", respectively, unless otherwise specified. , "Acryloyl and / or metaacryloyl", "acrylic and / or methacrylic acid", "acrylic acid and / or methacrylic acid", "acrylate and / or methacrylate", or "acrylamide and / or metaacrylamide" .. Further, "CI" means a color index (CI; The Society of Dyers and Colorists). The polymerizable unsaturated group is an ethylenically unsaturated double bond.
The molecular weight of the compound in the present invention is a value calculated by calculation or a molecular weight measured by ESI-MS (electrospray ionization mass spectrometry) for a low molecular weight compound whose molecular weight can be specified. For the compound to have, it is a weight average molecular weight in terms of polystyrene measured by gel permeation chromatography when tetrahydrofuran is used as a solvent.

<Photosensitive coloring composition>
The present invention is a photosensitive coloring composition containing a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D).
The polymerizable compound (C) is a photosensitive coloring composition containing an acid group-containing aromatic urethane (meth) acrylate (C1) and a lactone-modified (meth) acrylate (C2).

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

The colorant (A) is not particularly limited and may be any of a pigment and a dye, but a pigment is preferable because the color filter is required to have light resistance, heat resistance, and solvent resistance.

(Pigment)
The pigment is not particularly limited, and examples thereof include compounds classified as pigments in the color index.

Specific examples of the red pigment that can be used in the present invention include C.I. 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: 1,109,112,113,114,122,123,144,146,147,149,1511 166,168,169,170,172,173,174,175,176,177,178,179,181,184,185,187,188,190,193,194,200,202,206,207,208, 209,210,214,216,220,221,224,230,231,232,233,235,236,237,238,239,242,243,245,247,249,250,251,253,254 255,256,257,258,259,260,262,263,264,265,266,267,268,269,270,271,272,273,274,275,276,277,278,279,280, 281,282,283,284,285,286,287,291,295,296, pigments described in JP-A-2014-134712, pigments described in Japanese Patent No. 6368844, and the like can be mentioned. Among these, from the viewpoint of heat resistance, light resistance, and transmittance, C.I. I. Pigment Red 48: 1,122,177,224,242,269,254,291,295,296, the pigment described in JP-A-2014-134712, and the pigment described in Japanese Patent No. 6368844 are preferable. C. I. Pigment Red 177,254,291,295,296, the pigment described in JP-A-2014-134712, and the pigment described in Japanese Patent No. 6368844 are particularly preferable.

Specific examples of the orange pigment that can be used in the present invention include C.I. I. Pigment Orange 36, 38, 43, 64, 71, 73 and the like.

Specific examples of the yellow pigment that can be used in the present invention include C.I. I. Pigment Yellow 1,2,3,4,5,6,10,12,13,14,15,16,17,18,24,31,32,34,35,35: 1,36,36: 1, 37,37: 1,40,42,43,53,55,60,61,62,63,65,73,74,77,81,83,93,94,95,97,98,100,101, 104,106,108,109,110,113,114,115,116,117,118,119,120,123,126,127,128,129,138,139,147,150,151,152,153 154,155,156,161,162,164,166,167,168,169,170,171,172,173,174,175,176,177,179,180,181,182,185,187,188, Examples thereof include pigments described in 192,193,194,196,198,199,213,214,231,233, and Japanese Patent Application Laid-Open No. 2012-226110. Among these, C.I. I. Pigment Yellow 138,139,150,185,231,233, the pigment described in JP2012-226110A is preferable.

Specific examples of the green pigment that can be used in the present invention include C.I. I. Pigment Green 1,2,4,7,8,10,13,14,15,17,18,19,26,36,37,45,48,50,51,54,55,58,59,62, 63 and the like can be mentioned. Among these, C.I. I. Pigment greens 36, 58, 59, 62 and 63 are preferred.

Specifically, the blue pigment that can be used in the present invention is C.I. I. Pigment Blue 1,1: 2,9,14,15,15: 1,15: 2,15: 3,15: 4,15: 6,16,17,19,25,27,28,29,33, Examples thereof include 35, 36, 56, 56: 1,60, 61, 61: 1,62,63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, 79 and the like. Among these, C.I. I. Pigment Blue 15,15: 1,15: 2,15: 3,15: 4,15: 6 is preferred.

Specifically, the purple pigment that can be used in the present invention is C.I. I. Pigment Violet 1,1: 1,2,2: 2,3,3: 1,3: 3,5,5: 1,14,15,16,19,23,25,27,29,31,32, 37, 39, 42, 44, 47, 49, 50 and the like can be mentioned. Among these, C.I. I. Pigment Violet 19, 23 is preferred.

Specifically, the black pigment that can be used in the present invention is C.I. I. Pigment Black 1,6,7,12,20,31 and the like.

In the photosensitive coloring composition of the present invention, an inorganic pigment can also be used as the colorant (A). For example, titanium oxide, barium sulfate, zinc flower, lead sulfate, yellow lead, zinc yellow, red iron oxide (III), cadmium red, ultramarine blue, dark blue, chromium oxide green, cobalt green, amber, synthetic iron black, etc. Can be mentioned.

(dye)
The dye is not particularly limited, and examples thereof include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, medium dyes, building dyes, and sulfur dyes. Further, these derivatives or a lake pigment obtained by converting a dye into a lake may be used.

Further, an acidic dye having an acidic group such as sulfonic acid or carboxylic acid, or in the case of a direct dye form, an inorganic salt of the acidic dye, an acidic dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, Alternatively, a salt-forming compound with a nitrogen-containing compound such as a primary amine compound, or chloride-forming using a resin component having these functional groups to be used as a salt-forming compound, or sulfonamide formation and use as a sulfonic acid amide compound. It is preferable that the colored composition has excellent toughness because it has excellent resistance.
Further, a salt-forming compound of an acid dye and a compound having an onium base is also preferable because it has excellent fastness, and more preferably, the compound having an onium base is a resin having a cationic group in the side chain.

In the case of the basic dye form, it can be used by chlorinating with an organic acid, perchloric acid or a metal salt thereof. Among them, the salt-forming compound of the basic dye is preferable because it has excellent resistance and compatibility with the pigment, and further, the basic dye and the organic sulfonic acid, the organic sulfuric acid, and the fluorine group-containing phosphorus, which are counter components that act as counter ions, are preferable. It is possible to use a salt-forming compound obtained by salting an anionic compound, a fluorine group-containing boron anionic compound, a cyano group-containing nitrogen anion compound, an anion compound having a conjugated base of an organic acid having a halogenated hydrocarbon group, or an acidic dye. It is more preferable.

Further, when the dye skeleton has a polymerizable unsaturated group, the dye can be a dye having excellent resistance, which is preferable.

The chemical structure of the dye includes, for example, azo dye, disazo dye, azomethin dye (Indoaniline dye, Indophenol dye, etc.), Dipyrromethene dye, Kinon dye (benzoquinone dye, naphthoquinone dye, anthraquinone). Dyes, anthrapyridone dyes, carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acrydin dyes, etc.), quinoneimine dyes (oxazine dyes, thiadine dyes, etc.), azine dyes. Dyes, polymethine dyes (oxonol dyes, merocyanine dyes, allylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone Examples of dye structures are derived from dyes selected from dyes such as dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and their metal complex dyes. , Especially not limited to these.

Among these dye structures, from the viewpoint of color characteristics such as hue, color separability, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and squaryliums. Dye structures derived from dyes selected from dyes selected from dyes, quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferable, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are preferable. A dye structure derived from a dye selected from the dyes is more preferable. For specific dye compounds that can form a dye structure, see "New Edition Dye Handbook" (Society of Synthetic Organic Chemistry; Maruzen, 1970), "Color Index" (The Society of Dyeers and colorists), "Dye Handbook" (Okawara et al.) Hen; Kodansha, 1986).

The colorant (A) can be used alone or in combination of two or more.

The content of the colorant (A) is preferably 5 to 70% by mass, more preferably 10 to 60% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition.

(Pigment miniaturization)
The pigment is preferably used in a finely divided form. The miniaturization method is not particularly limited, and for example, wet grinding, dry grinding, and dissolution precipitation method can be used. Among these, the salt milling treatment by the kneader method, which is one of the wet grinding methods, is preferable. The average primary particle size determined by the TEM (transmission electron microscope) of the finely divided pigment is preferably 5 to 90 nm. From the viewpoint of dispersibility and contrast ratio, the average primary particle size is more preferably 10 to 70 nm.

Salt milling is a machine that heats a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent using a kneader such as a kneader, a 2-roll mill, a 3-roll mill, a ball mill, an attritor, and a sand mill. After kneading, the water-soluble inorganic salt and the water-soluble organic solvent are removed by washing with water. The water-soluble inorganic salt acts as a crushing aid, and the pigment is crushed by utilizing the high hardness of the inorganic salt during salt milling. By optimizing the conditions for the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

Examples of the water-soluble inorganic salt include sodium chloride, potassium chloride, sodium sulfate and the like, and sodium chloride (salt) is preferable from the viewpoint of price. The amount of the water-soluble inorganic salt used is preferably 50 to 2,000 parts by mass, more preferably 300 to 1,000 parts by mass with respect to 100 parts by mass of the pigment, from the viewpoints of both treatment efficiency and production efficiency.

The water-soluble organic solvent has a function of wetting 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 easily evaporates, a high boiling point solvent having a boiling point of 120 ° C. or higher is preferable 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 and the like are used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by mass, more preferably 50 to 500 parts by mass with respect to 100 parts by mass of the pigment.

If necessary, a resin may be added to the salt milling treatment. The type of the resin is not particularly limited, and examples thereof include a natural resin, a modified natural resin, a synthetic resin, and a synthetic resin modified with a natural resin. Among these, it is preferable that it is solid at room temperature, is insoluble in water, and is partially soluble in the above organic solvent. The amount of the resin added is preferably 2 to 200 parts by mass with respect to 100 parts by mass of the pigment.

[Alkali-soluble resin (B)]
The photosensitive composition of the present invention contains an alkali-soluble resin (B). As a result, the resistance of the cured film such as heat resistance and chemical resistance is improved.

The alkali-soluble resin (B) is not particularly limited, and a known resin can be used.

The alkali-soluble resin (B) can be classified into a non-photosensitive alkali-soluble resin and a photosensitive alkali-soluble resin. The alkali-soluble resin (B) 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 the like, and among these, a carboxyl group is preferable.
Further, the alkali-soluble resin (B) can contain a thermosetting group such as an epoxy group or an oxetanyl group.

(Non-photosensitive alkali-soluble resin)
The non-photosensitive alkali-soluble resin is, for example, an acrylic resin having an acidic group, an α-olefin / (anhydrous) maleic acid copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth) acrylic acid copolymer, and the like. Alternatively, isobutylene / (anhydrous) maleic acid copolymer and the like can be mentioned. Among these, an acrylic resin having an acidic group and a styrene / styrene sulfonic acid copolymer are preferable.

(Photosensitive alkali-soluble resin)
The photosensitive alkali-soluble resin is an alkali-soluble resin having a polymerizable unsaturated group. As the photosensitive alkali-soluble resin, for example, a resin synthesized by the method (i) or (ii) shown below is preferable. By curing with active energy rays, the resin is three-dimensionally crosslinked to improve the crosslink density and chemical resistance.

[Method (i)]
In method (i), for example, first, an epoxy group-containing monomer and a polymer of other monomers are synthesized. Next, a method of adding a monocarboxyl group-containing monomer to the epoxy group of the polymer and reacting the generated hydroxyl group with a polybasic acid anhydride to obtain a photosensitive alkali-soluble resin can be mentioned.

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 can be mentioned. Among these, glycidyl (meth) acrylate is preferable 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, and t-. Butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, stearyl (meth) acrylate, lauryl (meth) acrylate, tetrahydrofurfuryl (meth) acrylate, isobornyl (meth) acrylate, phenyl (meth) Acrylate, benzyl (meth) acrylate, phenoxyethyl (meth) acrylate, phenoxydiethylene glycol (meth) acrylate, methoxypolypropylene glycol (meth) acrylate, 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 (Meta) acrylates such as PO-modified (meth) acrylates;
(Meta) acrylamides such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, N, N-diethyl (meth) acrylamide, N-isopropyl (meth) acrylamide, diacetone (meth) acrylamide, or acryloyl morpholine. ;
Styrene, or styrenes such as α-methylstyrene;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;
Vinyl acetate, or fatty acid vinyls such as vinyl propionate;
Cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimideethane 1,6-bismaleimidehexane, 3-maleimidepropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidecoumarin, 4,4'-Bismaleimide diphenylmethane, bis (3-ethyl-5-methyl-4-maleimidephenyl) methane, N, N'-1,3-phenylenedi maleimide, N, N'-1,4-phenylenedi 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-maleimidebenzoate, N-succinimidyl-3-maleimidepropionate, N-succinimidyl-4-maleimidebutyrate, N-succinimidyl N-substituted maleimides such as -6-maleimide hexanoate, N- [4- (2-benzoimidazolyl) phenyl] maleimide, 9-maleimide acrydin;
2- (Meta) acryloyloxyethyl acid phosphate, a phosphoric acid ester group-containing simple compound such as a compound obtained by reacting the hydroxyl group of a hydroxyl group-containing monomer described later with a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid. Esters are mentioned and can be used alone or in combination of two or more.

The monocarboxyl group-containing monomer is, for example, (meth) acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl of (meth) acrylic acid, alkoxyl, halogen, nitro, cyano substituted. Examples thereof include monocarboxylic acids such as the body, which can be used alone or in combination of two or more.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride and the like, and they can be used alone or in combination of two or more. Further, if necessary, a tricarboxylic acid dianhydride such as trimellitic acid anhydride and a tetracarboxylic acid dianhydride such as pyromellitic acid anhydride can be used to hydrolyze the remaining anhydride group.

Further, as a method similar to the method (i), for example, a carboxyl group-containing monomer and a polymer of other monomers are synthesized. Next, a method of adding an epoxy group-containing monomer to a part of the carboxyl group of the polymer to obtain a photosensitive alkali-soluble resin can be mentioned.

[Method (ii)]
The method (ii) synthesizes, for example, a polymer of a hydroxyl group-containing monomer, a monocarboxyl group-containing monomer, and other monomers. Next, a method of reacting the hydroxyl group of the polymer with the isocyanate group of the isocyanate group-containing monomer can be mentioned.

The hydroxyl group-containing monomer is, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol mono (meth). Examples thereof include hydroxyalkyl methacrylates such as acrylate or cyclohexanedimethanol mono (meth) acrylate. Further, a polyether mono (meth) acrylate obtained by superpolymerizing hydroxyalkyl (meth) acrylate with ethylene oxide, propylene oxide, and / or butylene oxide, poly γ-valerolactone, poly ε-caprolactone, and / or poly. Polyester mono (meth) acrylate to which 12-hydroxystearic acid or the like is added can also be mentioned. These can be used alone or in combination of two or more. Among these, 2-hydroxyethyl methacrylate and glycerol mono (meth) acrylate are preferable in terms of preventing foreign substances from being generated in the coating film. Further, glycerol mono (meth) acrylate is preferable in terms of light sensitivity.

Examples of the isocyanate group-containing monomer include 2- (meth) acryloylethyl isocyanate, 2- (meth) acryloyloxyethyl isocyanate, 1,1-bis [methacryloyloxy] ethyl isocyanate, and the like, alone or in combination of two or more. Can be used in combination.

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

The alkali-soluble resin (B) can be synthesized by using the above-mentioned monomers alone or by using two or more kinds.

The weight average molecular weight (Mw) of the alkali-soluble resin (B) is preferably 2,000 to 40,000, more preferably 3,000 to 3,000, and 4,000 to 20,000 from the viewpoint of developability. Especially preferable. Further, the value of the ratio (Mw / Mn) to the number average molecular weight (Mn) is preferably 10 or less. The appropriate weight average molecular weight (Mw) improves the adhesion to the substrate and the alkali development solubility.

The acid value of the alkali-soluble resin (B) is preferably 50 to 200 mgKOH / g, more preferably 70 to 180 mgKOH / g, and even more preferably 90 to 170 mgKOH / g. Adhesion to the substrate and alkali development solubility are improved by an appropriate acid value.

The alkali-soluble resin (B) can be used alone or in combination of two or more.

The content of the alkali-soluble resin (B) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass with respect to 100 parts by mass of the colorant (A).

[Polymerizable compound (C)]
The photosensitive coloring composition of the present invention contains an acid group-containing aromatic urethane (meth) acrylate (C1) and a lactone-modified (meth) acrylate (C2) as the polymerizable compound (C). Here, examples of the acid group include a carboxyl group, a sulfonic acid group, and a phosphoric acid group.
By containing the acid group-containing aromatic urethane (meth) acrylate (C1), the urethane-bonded portion having a highly rigid aromatic ring structure suppresses shrinkage during curing, suppresses the generation of wrinkles, and the acid group is alkaline. It is considered that the solubility of the developing solution is improved and the development is completed in a short time, so that the cured film is suppressed from being chipped or peeled off. Furthermore, by containing lactone-modified (meth) acrylate (C2), the lactone-structured portion with high hydrophobicity and thermal stability weakens the affinity between water and the film during alkaline development, suppresses water stains, and suppresses water stains. It is considered that the residual film ratio is improved by suppressing decomposition during post-baking. By combining these, it is said that a photosensitive coloring composition having less wrinkles on the surface of the pattern, suppressing water stains after development, and having excellent pattern forming properties (adhesion, shape, residual film ratio) was obtained. Infer.

(Acid group-containing aromatic urethane (meth) acrylate (C1))
The acid group-containing aromatic urethane (meth) acrylate (C1) is not particularly limited, and known ones can be used. For example, a compound obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate having an aromatic ring structure, and then adding a mercapto compound having a carboxyl group to the product.
A compound in which a polyfunctional isocyanate having an aromatic ring structure is reacted with a polyhydric alcohol, a (meth) acrylate having a hydroxyl group is reacted, and then a mercapto compound having a carboxyl group is added to the product, or a compound.
Examples thereof include compounds in which a polyhydric alcohol having a carboxyl group is reacted with a polyfunctional isocyanate having an aromatic ring structure, and then a (meth) acrylate having a hydroxyl group is reacted.

The (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, and 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, Examples thereof include glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy (meth) acrylate, and a hydroxyl group-containing polyol polyacrylate.

The polyfunctional isocyanate having the aromatic ring structure is, for example, 1,5-naphthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, 4,4'-dibenzylisocyanate, dialkyldiphenylmethane. Diisocyanate, tetraalkyldiphenylmethane diisocyanate, 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, xylylene diisocyanate, m-tetramethylxylylene diisocyanate, 4 , 4-Diphenylmethane diisocyanate, bis-chloromethyl-diphenylmethane-diisocyanate, 2,6-diisocyanate-benzyl chloride, bis (isocyanatemethyl) benzene and the like. Further, these burette bodies, isocyanate nurate bodies, trimethylolpropane adduct bodies and the like can be mentioned.

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

The polyhydric alcohol having a carboxyl group includes, for example, the polyhydric alcohol, polybasic acid or an anhydride thereof (for example, succinic acid, succinic anhydride, fumaric acid, fumaric anhydride, tetrahydrophthalic anhydride, etc.) and dimethyrol. Examples thereof include compounds obtained by reacting propionic acid.

The number of polymerizable unsaturated groups of the acid group-containing aromatic urethane (meth) acrylate (C1) is preferably 3 to 15 and more preferably 5 to 12 from the viewpoint of suppressing wrinkles and forming a pattern.

The molecular weight of the acid group-containing aromatic urethane (meth) acrylate (C1) is preferably 500 to 5,000, more preferably 500 to 3,000, from the viewpoint of suppressing wrinkles and forming a pattern. ..

The acid group-containing aromatic urethane (meth) acrylate (C1) can be used alone or in combination of two or more.

(Lactone-modified (meth) acrylate (C2))
The lactone-modified (meth) acrylate (C2) is not particularly limited as long as it has a lactone-modified structure in the molecule, but is not particularly limited, but is limited to trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, and pentaethi. It is obtained by esterifying polyhydric alcohols such as thritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine with (meth) acrylic acid and ε-caprolactone or other lactones. Among them, the compound represented by the following general formula (1) is preferable.

（一般式（１）中、６個のＲは全て下記一般式（２）で表される基であるか、または６個のＲのうち１～５個が下記一般式（２）で表される基であり、残りが下記一般式（３）で表される基である。） General formula (1)

(In the general formula (1), all 6 Rs are groups represented by the following general formula (2), or 1 to 5 of the 6 Rs are represented by the following general formula (2). The rest is the group represented by the following general formula (3).)

（一般式（２）中、Ｒ^１は水素原子、またはメチル基を表し、ｍは１、または２の整数であり、＊は結合手である。） General formula (2)

(In the general formula (2), R ¹ represents a hydrogen atom or a methyl group, m is an integer of 1 or 2, and * is a bond.)

（式中、Ｒ^１は水素原子、またはメチル基を表し、＊は結合手である。） General formula (3)

(In the formula, R ¹ represents a hydrogen atom or a methyl group, and * is a bond.)

The lactone-modified (meth) acrylate (C2) is commercially available, for example, as the KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd. Number of groups represented by 2) = 2, compound in which R ¹ is all hydrogen atom), DPCA-30 (in general formulas (1) to (3), m = 1, represented by general formula (2) Number of groups = 3, DPCA-60 (a compound in which all R ^1s are hydrogen atoms), m = 1 in the general formulas (1) to (3), the number of groups represented by the general formula (2) = 6, DPCA-120 (a compound in which all R ¹ are hydrogen atoms), m = 2, in the general formulas (1) to (3), the number of groups represented by the general formula (2) = 6, R ¹ is Compounds that are all hydrogen atoms) and the like.

The lactone-modified (meth) acrylate (C2) has m = 1 in the general formulas (1) to (3) and the number of groups represented by the general formula (2) from the viewpoint of suppressing water stains and forming a pattern. = 2 to 6, a compound in which all R ¹ is a hydrogen atom is preferable, and in the general formulas (1) to (3), m = 1, the number of groups represented by the general formula (2) = 2 or 3, R. A compound in which ¹ is all hydrogen atoms is more preferable.

The total content of the acid group-containing aromatic urethane (meth) acrylate (C1) and the lactone-modified (meth) acrylate (C2) is a polymerizable compound from the viewpoint of suppressing wrinkles, suppressing water stains, and forming a pattern. C) Of 100% by mass, it is preferably 20% by mass or more, more preferably 30 to 80% by mass, and particularly preferably 40 to 70% by mass.

The mass ratio of the acid group-containing aromatic urethane (meth) acrylate (C1) to the lactone-modified (meth) acrylate (C2) is 80:20 from the viewpoint of suppressing wrinkles, suppressing water stains, and forming a pattern. It is preferably from 20:80, more preferably from 70:30 to 30:70.

The lactone-modified (meth) acrylate (C2) can be used alone or in combination of two or more.

(Aliphatic urethane (meth) acrylate (C3) and alicyclic urethane (meth) acrylate (C4))
The photosensitive coloring composition of the present invention, as the polymerizable compound (C), further, from the viewpoint of suppressing wrinkles, further, an aliphatic urethane (meth) acrylate (C3) and an alicyclic urethane (meth) acrylate (C4). It is preferable to contain at least one selected from the group consisting of.
At least one selected from the group consisting of highly flexible aliphatic or aliphatic urethane (meth) acrylate (C3) having an alicyclic structure and alicyclic urethane (meth) acrylate (C4), and rigidity. By using in combination with an acid group-containing aromatic urethane (meth) acrylate (C1) having a high aromatic structure, shrinkage during curing can be further suppressed.

Above all, from the viewpoint of suppressing wrinkles, it is more preferable to contain an aliphatic urethane (meth) acrylate (C3).

The aliphatic urethane (meth) acrylate (C3) is not particularly limited, and known ones can be used. For example, a compound obtained by reacting a (meth) acrylate having a hydroxyl group with a polyfunctional isocyanate having an aliphatic structure, or a polyhydric alcohol reacting with a polyfunctional isocyanate having an aliphatic structure, and further having a hydroxyl group (meth). ) Examples thereof include compounds obtained by reacting with acrylate.

The (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, and 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, Examples thereof include glycerol acrylate methacrylate, glycerol dimethacrylate, 2-hydroxy-3-acryloylpropyl methacrylate, a reaction product of an epoxy group-containing compound and a carboxy (meth) acrylate, and a hydroxyl group-containing polyol polyacrylate.

Examples of the polyfunctional isocyanate having the aliphatic structure include butane-1,4-diisocyanate, hexamethylene diisocyanate, isopropylene diisocyanate, methylene diisocyanate, and 2,2,4-trimethylhexamethylene diisocyanate. Further, these burette bodies, isocyanate nurate bodies, trimethylolpropane adduct bodies and the like can be mentioned.

The alicyclic urethane (meth) acrylate (C4) is not particularly limited, and known ones can be used. For example, it can be obtained by changing the polyfunctional isocyanate having an aliphatic structure of the above-mentioned aliphatic urethane (meth) acrylate (C3) to a polyfunctional isocyanate having an alicyclic structure.

The polyfunctional isocyanate having the alicyclic structure is, for example, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dimethylcyclohexyldiisocyanate, methylcyclohexyldiisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis (isocyanate). Examples thereof include methyl) cyclohexane, methylcyclohexanediisocyanate, norbornane diisocyanate, and bis (isocyanatemethyl) cyclohexane. Further, these burette bodies, isocyanate nurate bodies, trimethylolpropane adduct bodies and the like can be mentioned.

The number of polymerizable unsaturated groups of the aliphatic urethane (meth) acrylate (C3) and the alicyclic urethane (meth) acrylate (C4) is preferably 4 to 15 from the viewpoint of suppressing wrinkles and forming a pattern, preferably 6 to 6. Twelve are more preferable.

The molecular weight of the aliphatic urethane (meth) acrylate (C3) and the alicyclic urethane (meth) acrylate (C4) is preferably 500 to 5,000, preferably 500 to 5,000, from the viewpoint of suppressing wrinkles and forming a pattern. More preferably, it is 3,000.

The aliphatic urethane (meth) acrylate (C3) and the alicyclic urethane (meth) acrylate (C4) can contain an acid group. As the method for containing the acid group, the same method as the above-mentioned acid group-containing aromatic urethane (meth) acrylate (C1) can be used.

The ratio of the mass of the acid group-containing aromatic urethane (meth) acrylate (C1) to the total amount of the aliphatic urethane (meth) acrylate (C3) and the alicyclic urethane (meth) acrylate (C4) suppresses wrinkles. From the viewpoint of pattern formability, it is preferably 90:10 to 50:50, and more preferably 85:15 to 65:35.

The aliphatic urethane (meth) acrylate (C3) and the alicyclic urethane (meth) acrylate (C4) can be used alone or in combination of two or more.

(Polymerizable compound (C5) other than (C1) to (C4))
The photosensitive coloring composition of the present invention can contain a polymerizable compound (C5) other than (C1) to (C4) (hereinafter, also referred to as another polymerizable compound (C5)).

Examples of the other polymerizable compound (C5) include methyl (meth) acrylate, ethyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, cyclohexyl (meth) acrylate, and β-. Carboxyethyl (meth) acrylate, polyethylene glycol di (meth) acrylate, 1,6-hexanedioldi (meth) acrylate, triethylene glycol di (meth) acrylate, polypropylene glycol di (meth) acrylate, tricyclodecanedimethanol di. (Meta) acrylate, ethoxylated bisphenol A di (meth) acrylate, 9,9-bis [4- (2-hydroxyethoxy) phenyl] full orange acrylate, trimethylol propanetri (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, ditrimethylol propanetetra (meth) acrylate, pentaerythritol tri (meth) acrylate, pentaerythritol tetra (meth) acrylate, 1,6-hexanedioldiglycidyl ether di (meth) acrylate, bisphenol A diglycidyl ether di Of (meth) acrylate, neopentyl glycol diglycidyl ether di (meth) acrylate, dipentaerythritol hexa (meth) acrylate, dipentaerythritol penta (meth) acrylate, tricyclodecanyl (meth) acrylate, methylolated melamine Various acrylic acid esters such as (meth) acrylic acid ester and epoxy (meth) acrylate, and methacrylate esters, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth) acrylamide, N-hydroxy. Examples thereof include methyl (meth) acrylamide, N-vinylformamide, acrylonitrile and the like. Among these, those having 5 or more polymerizable unsaturated groups are preferable from the viewpoint of pattern formation.

Other commercially available products of the polymerizable compound (C5) 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, Aronix M-303, M-305, M-306, M-309 manufactured by Toagosei Co., Ltd. , M-310, M-321, M-325, M-350, M-360, M-313, M-315, M-400, M-402, M-403, M-404, M-405, M -406, M-450, M-452, M-408, M-211B, M-101A, M-5300, M-5400, M-5700, M-510, M-520, M-521, Osaka Gas Chemicals OGSOL EA-0200, EA-0300, GA-5060P, GA-2800, Miwon Specialty Chemical Co., manufactured by the same company. , Miramer HR6060, 6100, 6200 manufactured by Ltd., Viscoat # 2500P manufactured by Osaka Organic Co., Ltd., NK Ester ABE-300, A-DOG, A-DCP, A-BPE-4 manufactured by Shin Nakamura Chemical Industry Co., Ltd. EBECRY 40, 130, 140, 145 and the like manufactured by Ornex Co., Ltd. can be mentioned.

The content of the polymerizable compound (C) is preferably 5 to 50% by mass, more preferably 5 to 30% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition.

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

The photopolymerization initiator (D) is not particularly limited as long as it is a compound capable of initiating the polymerization of the polymerizable compound (C) by light, and a known photopolymerization initiator can be used. For example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexylphenylketone, 2-Methyl-1- [4- (Methylthio) Phenyl] -2-morpholinopropane-1-one, 2- (dimethylamino) -1- [4- (4-morpholino) phenyl] -2- (Phenylmethyl) ) -1-Butanone, or 2- (dimethylamino) -2-[(4-methylphenyl) methyl] -1- [4- (4-morpholinyl) phenyl] -1-butanone and other acetophenone compounds;
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) Methyl) -6-styryl-s-triazine, 2- (naphtho-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2- (4-methoxy-naphtho-1-yl) -4 , 6-Bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine, or 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine. System compounds;
1,2-octanedione, 1- [4- (phenylthio) phenyl-, 2- (O-benzoyloxime)], or etanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazole 3-Il]-, 1- (O-acetyloxime) and other oxime compounds;
Acylphosphine compounds such as bis (2,4,6-trimethylbenzoyl) phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide;
Examples thereof include quinone-based compounds such as 9,10-phenanthrene quinone, camphorquinone, and ethylanthraquinone; borate-based compounds; carbazole-based compounds; imidazole-based compounds; and titanocene-based compounds.
Among these, the oxime-based compound (D1) and the acetophenone-based compound (D2) are preferable, and the oxime-based compound (D1) is more preferable, from the viewpoint of pattern formation.

(Oxime compound (D1))
Examples of the oxime compound (D1) include an oxime compound (D1-1) containing one oxime group in one molecule and an oxime compound (D1-2) containing two oxime groups in one molecule. From the viewpoint of pattern forming property, an oxime-based compound (D1-2) containing two oxime groups in one molecule is particularly preferable.

[Oxime-based compound (D1-1) containing one oxime group in one molecule]
The oxime-based compound (D1-1) containing one oxime group in one molecule is, for example, IRGACURE OXE-01, 02, 03, 04 manufactured by BASF, and ADEKA ARCLUS N-1919, NCI manufactured by ADEKA. -730, 831,930, TRONLY TR-PBG-301, 304, 305, 309, 314, 358, 380, 365, 610, 3054, 3057, OMNIRA D1312, 1314, manufactured by Changzhou Strong New Materials Co., Ltd. Examples thereof include 1316, SPI-02, 03, 04, 05, 06, 07 manufactured by Samyan Corporation, DFI-020, 066, EOX-01 manufactured by Daito Chemix, and the like.

[Oxime-based compound containing two oxime groups in one molecule (D1-2)]
The oxime compound (D1-2) containing two oxime groups in one molecule is described in, for example, JP-A-2005-215378, JP-A-2011-105713, JP-A-2017-523465 and the like. Examples include compounds. Among them, the compound represented by the following general formula (4) is preferable.

（一般式（４）中、Ｘ_１及びＸ_２は、各々独立にカルボニル結合（－ＣＯ－）又は単結合を表す。Ｒ_１は、炭素数１～２０のアルキル基を表し、Ｒ_２及びＲ_３は、個々独立に水素原子、炭素数１～２０のアルキル基、炭素数２～３０の複素環、炭素数６～３０のアリール基、又は炭素原子数７～３０のアリールアルキル基を表す。Ｒ_４及びＲ_５は、各々独立に炭素数１～２０のアルキル基、炭素原子数２～３０の複素環基、炭素数６～３０のアリール基、又は炭素数７～３０のアリールアルキル基を表す。） General formula (4)

(In the general formula (4), X ₁ and X ₂ each independently represent a carbonyl bond (-CO-) or a single bond. R ₁ represents an alkyl group having 1 to 20 carbon atoms, and R ₂ and R are represented. Reference numeral ₃ independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, a heterocycle having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. R ₄ and R ₅ each independently have an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an arylalkyl group having 7 to 30 carbon atoms. show.)

In the general formula (4), X ₁ and X ₂ each independently represent a carbonyl bond (-CO-) or a single bond. Among them, from the viewpoint of solubility in an organic solvent, at least one of X ₁ and X ₂ is preferably a carbonyl bond (-CO-), and X ₁ and X ₂ are carbonyl bonds (-CO-). It is more preferable to have.

In the general formula (4), R ₁ represents an alkyl group having 1 to 20 carbon atoms.
The alkyl group having 1 to 20 carbon atoms may be a linear group, a branched group, a cyclic group, or a combination of these alkyl groups, and an alkyl substituted with a halogen atom, an amino group, a nitro group, or the like. It may be a group. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group. , Nonyl group, decyl group, cyclopentyl group, cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group and the like. Among these, an ethyl group, a propyl group and an isopropyl group are preferable.

In the general formula (4), R ₂ and R ₃ are independently hydrogen atoms, alkyl groups having 1 to 20 carbon atoms, heterocycles having 2 to 30 carbon atoms, aryl groups having 6 to 30 carbon atoms, or carbon atoms. Represents an arylalkyl group of number 7-30.
The alkyl group having 1 to 20 carbon atoms may be a linear group, a branched group, a cyclic group, or a combination of these alkyl groups, and an alkyl substituted with a halogen atom, an amino group, a nitro group, or the like. It may be a group. For example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, t-butyl group, amyl group, isoamyl group, pentyl 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. Among these, a pentyl group, a hexyl group, a heptyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group, a cyclohexylmethyl group and a cyclohexylmethyl group are preferable.
Examples of the heterocyclic group having 2 to 30 carbon atoms include a pyridyl group, a pyrimidyl group, a frill group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group and a morpholinyl group.
Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group and the like, and the aryl group is substituted with a halogen atom, an amino group, a nitro group and the like. It may be an aryl group.
Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, α-methylbenzyl, α, α-dimethylbenzyl group, phenylethyl group and the like, and are substituted with a halogen atom, an amino group, a nitro group and the like. It may be a benzylalkyl group.

Among these, R ₂ and R ₃ are preferably linear alkyl groups having at least one carbon atom of 1 to 20 from the viewpoint of solubility in an organic solvent, and have solubility in an organic solvent. From the viewpoint of suppressing water stains, a linear alkyl group having 1 to 20 carbon atoms and a cyclic alkyl group having 1 to 20 carbon atoms are more preferable.

In the general formula (4), R ₄ and R ₅ each independently have an alkyl group having 1 to 20 carbon atoms, a heterocyclic group having 2 to 30 carbon atoms, an aryl group having 6 to 30 carbon atoms, or 7 carbon atoms. Represents ~ 30 arylalkyl groups.
The alkyl group having 1 to 20 carbon atoms may be a linear group, a branched group, a cyclic group, or a combination of these alkyl groups, and an alkyl substituted with a halogen atom, an amino group, a nitro group, or the like. It may be a group. For example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a t-butyl group, an amyl group, an isoamyl group, a pentyl group, a hexyl group, a cyclopentyl group, a cyclopentylmethyl group, a cyclohexyl group and the like can be mentioned. .. Among these, a methyl group, an ethyl group, a propyl group and an isopropyl group are preferable from the viewpoint of reactivity.
Examples of the heterocyclic group having 2 to 30 carbon atoms include a pyridyl group, a pyrimidyl group, a frill group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group and a morpholinyl group.
Examples of the aryl group having 6 to 30 carbon atoms include a phenyl group, a tolyl group, a xylyl group, an ethylphenyl group, a naphthyl group, an anthryl group and the like, and the aryl group is substituted with a halogen atom, an amino group, a nitro group and the like. It may be an aryl group. Among these, a phenyl group is preferable from the viewpoint of reactivity.
Examples of the arylalkyl group having 7 to 30 carbon atoms include a benzyl group, α-methylbenzyl, α, α-dimethylbenzyl group, phenylethyl group and the like, and a halogen atom, an amino group, a nitro group and the like. It may be a substituted arylalkyl group.

Among these, R ₄ and R ₅ are preferably a methyl group, an ethyl group, or a phenyl group, and more preferably a methyl group or an ethyl group from the viewpoint of reactivity.

The method for producing the compound represented by the general formula (4) is not particularly limited, and a known method can be used. For example, the method described in JP-A-2017-523465 can be used.

Hereinafter, specific examples of the oxime compound (D1-2) containing two oxime groups in one molecule will be shown. The present invention is not limited to these.

Chemical formula (5)

Chemical formula (6)

Chemical formula (7)

Chemical formula (8)

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

The content of the photopolymerization initiator (D) is preferably 0.5 to 50 parts by mass and 1 to 20 parts by mass with respect to 100 parts by mass of the colorant (A) from the viewpoint of photocurability and pattern forming property. Is more preferable, and 2 to 10% by mass is particularly preferable.

[Sensitizer (E)]
The photosensitive coloring composition of the present invention preferably contains a sensitizer (E) from the viewpoint of pattern forming property.

The sensitizer (E) is, for example, a chalcone compound, unsaturated ketones represented by dibenzalacetone, 1,2-diketone compounds represented by benzyl, camphorquinone, etc., benzoin compounds, fluorene. Polymethins such as phyllous compounds, naphthoquinone compounds, anthraquinone compounds, xanthene compounds, thioxanthene compounds, xanthone compounds, thioxanthone compounds, coumarin compounds, ketocoumarin compounds, cyanine compounds, merocyanine compounds, oxonor compounds, etc. Dyes, acridin-based compounds, azine-based compounds, thiazine-based compounds, oxazine-based compounds, indolin-based compounds, azulene-based compounds, azurenium-based compounds, squarylium-based compounds, porphyrin-based compounds, tetraphenylporphyrin-based compounds, triarylmethane-based compounds, Tetrabenzoporphyrin-based compounds, tetrapyrazinoporphyrazine-based compounds, phthalocyanine-based compounds, tetraazaporphyrazine-based compounds, tetraquinoxalyloporphyrazine-based compounds, naphthalocyanine-based compounds, subphthalocyanine-based compounds, pyririum-based compounds, thiopyrilium-based compounds. Examples thereof include compounds, tetraphyrin-based compounds, anurene-based compounds, spiropyran-based compounds, spiroxazine-based compounds, thiospiropyran-based compounds, metal allene complexes, organic ruthenium complexes, and benzophenone-based compounds. Among these, the thioxanthone-based compound (E1) or the benzophenone-based compound (E2) is preferable, and the benzophenone-based compound (E2) is more preferable, from the viewpoint of pattern formation.

(Thioxanthone compound (E1))
Examples of the thioxanthone compound (E1) include 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone and the like. Be done. Of these, 2,4-diethylthioxanthone is preferable.

(Benzophenone compound (E2))
Examples of the benzophenone compound (E2) include 4,4'-bis (dimethylamino) benzophenone, 4,4'-bis (diethylamino) benzophenone, 2-aminobenzophenone and the like. Of these, 4,4'-bis (diethylamino) benzophenone is preferred.

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

The content of the sensitizer (E) is preferably 150 to 400 parts by mass, preferably 150 to 300 parts by mass with respect to 100 parts by mass of the photopolymerization initiator (D) from the viewpoint of suppressing water stains and forming a pattern. Is more preferable.

[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 examples thereof include a dye derivative having an acidic group, a basic group, a neutral group, or the like as an 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 phosphate group, an amine salt thereof, or a basic substituent such as a sulfonamide group or a tertiary amino group at the terminal. Examples thereof include compounds having a neutral substituent such as a phenyl group and a phthalimidealkyl group.
Organic pigments include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, and benzoiso. Examples thereof include indol pigments such as indole, isoindolin pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, slene pigments, metal complex pigments, and azo pigments such as azo, disazo and polyazo.

Specifically, as the diketopyrrolopyrrole dye derivative, JP-A-2001-22520, International Publication No. 2009/081930, International Publication No. 2011/0526117, International Publication No. 2012/102399, JP-A-2017 156397, as phthalocyanine dye derivatives, JP-A-2007-226161, International Publication No. 2016/163351, JP-A-2017-165820, Patent No. 5735266, as anthraquinone-based dye derivatives, special Kaisho 63-264674, JP-A-09-272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, International Publication No. 2009/025325, Kinacridone-based As the dye derivative, JP-A-48-54128, JP-A-03-9961 and JP-A-2000-273383, and as the dioxazine-based dye derivative, JP-A-2011-162662, JP-A-2011-162662, the thiazine-indigo dye. As the derivative, JP-A-2007-314785, and as the triazine-based dye derivative, JP-A-61-246261, JP-A-11-19976, JP-A-2003-165922, JP-A-2003-168208. JP-A-2004-217842, JP-A-2007-314681, JP-A-2009-57478 as a benzoisoindole-based dye derivative, JP-A-2003-167112 as a quinophthalone-based dye derivative, JP. JP-A-2006-291194, JP-A-2008-31281, JP-A-2012-226110, and as naphthol-based dye derivatives, JP-A-2012-208329, JP-A-2014-5439, azo-based dyes. Derivatives are JP-A-2001-172520, JP-A-2012-1722092, acidic substituents are JP-A-2004-307854, and basic substituents are JP-A-2002-201377. Examples thereof include known dye derivatives described in JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404 and the like. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound, but the above-mentioned organic dye residue includes an acidic group, a basic group, and the like. A compound having a substituent such as a neutral group is synonymous with a dye derivative.

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

The content of the dye derivative (F) is preferably 1 to 20 parts by mass, more preferably 2 to 10 parts by mass with respect to 100 parts by mass of the colorant (A).

[Dispersed resin (G)]
The photosensitive composition of the present invention may contain a dispersion resin (G), if necessary.
The dispersion resin (G) is preferably a resin having an adsorbing group having a high affinity for the colorant (A). The adsorbent group preferably has at least one of a basic group and an acidic group, and preferably has an acidic group from the viewpoint of developability.

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

Examples of the acidic group include a carboxyl group, a phosphoric acid group, a sulfonic acid group and the like. Among these, a carboxyl group and a phosphoric acid group are preferable from the viewpoint of adsorptivity to pigments and developability.

The resin type of the dispersed resin (G) is, for example, a urethane resin, a polycarboxylic acid ester such as polyacrylate, an unsaturated polyamide, a polycarboxylic acid, a polycarboxylic acid (partial) amine salt, a polycarboxylic acid ammonium salt, or a polycarboxylic acid. Alkylamine salts, polysiloxanes, long-chain polyaminoamidophosphates, hydroxyl group-containing polycarboxylic acid esters and modified products thereof, amides formed by the reaction of poly (lower alkyleneimine) with polyesters having free carboxyl groups. Water-soluble such as (meth) acrylic acid-styrene copolymer, (meth) acrylic acid- (meth) acrylic acid ester copolymer, styrene-maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone, etc. Examples thereof include sex resins, water-soluble polymer compounds, polyester-based materials, modified polyacrylate-based compounds, ethylene oxide / propylene oxide-added compounds, and phosphoric acid ester-based compounds.

Examples of the structure of the dispersed resin (G) include a random structure, a block structure, a graft structure, a comb-shaped structure, and a star-shaped structure. Among these, a block structure or a comb-shaped structure is preferable from the viewpoint of dispersion stability.

Commercially available products of the dispersed resin (G) include, for example, Disperbyk-101,103,107,108,110,111,116,130,140,154,161,1622,163,164,165, manufactured by Big Chemie Japan. 166,167,168,170,171,174,180,181,182,183,184,185,190,2000,2001,2009,2010,2020,2025,205,2070,2095,2150,2155,2163 2164, or Anti-Terra-U203,204, or BYK-P104, P104S, 220S, or Lactimon, Lactimon-WS, or Bykumen, etc. , 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 56000, 76500 Etc., EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300 manufactured by BASF Japan. , 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. Ajisuper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Techno Co., Ltd. Examples thereof include the described resins.

The dispersed resin (G) can be used alone or in combination of two or more.

The content of the dispersion resin (G) is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass with respect to 100 parts by mass of the colorant (A) from the viewpoint of dispersion stability.

[Thermosetting compound (H)]
The photosensitive coloring composition of the present invention can contain a thermosetting compound (H). As a result, the thermosetting compound (H) reacts in the heating step, and the crosslink density is increased, so that the heat resistance is improved.

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

(Epoxy compound (H1))
The epoxy compound (H1) includes, 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, alkylaldehyde, benzaldehyde, alkyl-substituted benzaldehyde, hydroxybenzaldehyde, naphthaldehyde, glutaaldehyde, phthalaldehyde, crotonaldehyde, cinnamaldehyde, etc.) Polymerization of substances, phenols and various diene compounds (dicyclopentadiene, terpenes, vinylcyclohexene, norbornadiene, vinylnolbornene, tetrahydroinden, divinylbenzene, divinylbiphenyl, diisopropenylbiphenyl, butadiene, isoprene, etc.) Phenols and polycondensates of phenols and ketones (acetone, methylethylketone, methylisobutylketone, acetophenone, benzophenone, etc.), phenols and aromatic dimethanols (benzenedimethanol, α, α, α', α'- Polycondensate with benzenedimethanol, biphenyldimethanol, α, α, α', α'-biphenyldimethanol, etc.), phenols and aromatic dichloromethyls (α, α'-dichloroxylene, bischloromethylbiphenyl, etc.) Etc.), polycondensate of bisphenols and various aldehydes, glycidyl ether-based epoxy resin obtained by glycidylizing alcohols, alicyclic epoxy resin, heterocyclic epoxy resin, aliphatic epoxy resin, glycidylamine Examples thereof include a glycidyl ester-based epoxy resin and a glycidyl ester-based epoxy resin.

Commercially available products include, for example, Epicoat 807,815,825,827,828,190P,191P manufactured by Yuka Shell Epoxy, TECHMORE VG3101L manufactured by Mitsui Chemicals, EPPN-201, 501H, 502H manufactured by Nippon Kayaku Co., Ltd. EOCN-102S, 103S, 104S, 1020 Epicoat 1004, 1256 manufactured by Japan Epoxy Resin, JER1032H60, 157S65, 157S70, 152, 154, Serokiside 2021 manufactured by Daicel Chemical Industries, EHPE-3150, Denacol manufactured by Nagase Chemtex. EX-21,212,252,313,314,321,411,421,512,521,611,612,614,614B,622,711,721, TEPIC-L, H, S, etc. manufactured by Nissan Chemical Industries, Ltd. Can be mentioned.

The content of the epoxy compound (H1) is preferably 0.5 to 300 parts by mass, more preferably 1.0 to 50 parts by mass with respect to 100 parts by mass of the colorant (A) from the viewpoint of heat resistance of the cured film. preferable.

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

The monofunctional oxetane compound is, for example, (3-ethyloxetane-3-yl) methyl acrylate, (3-ethyloxetane-3-yl) methylmethacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3-. (2-Ethylhexyloxymethyl) oxetane, 3-ethyl-3- (phenoxymethyl) oxetane, 3-ethyl-3- (2-methacryloxymethyl) oxetane, 3-ethyl-3-{[3- (triethoxy) Cyril) propoxy] methyl} oxetane and the like.

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

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-oxa-nonane, 1,2-bis [(3-ethyl-3-oxetanylmethoxy) methyl] ethane, 1,3-bis [(3-ethyl-3-oxetanylmethoxy) methyl] propane, ethylene glyco-subis (3-Ethyl-3-oxetanylmethyl) ether, dicyclopentenylbis (3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis (3-ethyl-3-oxetanylmethyl) ether, tetraethyleneglycolbis (3) -Ethyl-3-oxetanylmethyl) ether, 1,4-bis (3-ethyl-3-oxetanylmethoxy) butane, 1,6-bis (3-ethyl-3-oxetanylmethoxy) hexane, polyethylene glycol bis (3-) Ethyl-3-oxetanylmethyl) ether, ethylene oxide (EO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, propylene oxide (PO) modified bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified hydrogenated bisphenol A bis (3-ethyl-3-oxetanylmethyl) ether, PO-modified hydrogenated bisphenol A-bis (3-ethyl-3-oxetanylmethyl) ether, EO-modified bisphenol F (3-ethyl-3-oxetanyl) Methyl) ether and the like can be mentioned.

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

Examples of the trifunctional or higher functional oxetane compound include pentaerythritol tris (3-ethyl-3-oxetanylmethyl) ether, pentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, and dipentaerythritol hexa (3-ethyl-3). -Oxetanylmethyl) ether, dipentaerythritol pentax (3-ethyl-3-oxetanylmethyl) ether, dipentaerythritol tetrakis (3-ethyl-3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol hexa (3-ethyl-) 3-oxetanylmethyl) ether, caprolactone-modified dipentaerythritol pentaxe (3-ethyl-3-oxetanylmethyl) ether, ditrimethylolpropanetetrakis (3-ethyl-3-oxetanylmethyl) ether, resin containing oxetane radical (3-ethyl-3-oxetanylmethyl) ether For example, a polymer obtained by radically polymerizing a (meth) acrylic monomer such as the oxetane-modified phenol novolak resin described in Patent No. 3783462 and the above-mentioned OXE-30 can be mentioned.

The content of the oxetane compound (H2) is preferably 0.5 to 50% by mass, more preferably 1 to 40% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition.

The 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 of 5.0 or more per melamine ring. If it has an appropriate number of methylol groups and ether groups, it is easy to obtain heat resistance that is not excessive or insufficient.

Commercially available products include, for example, Nikarac 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, Cymel 232, 235, 236, 238, 285, 300, 301, 303, 350, 370 manufactured by Nippon Cytec Industries Co., Ltd. and the like can be mentioned.

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

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

[Curing agent (curing accelerator)]
Since the photosensitive coloring composition of the present invention assists the curing of the thermosetting compound (H), a curing agent (curing accelerator) can be used in combination. Examples of the curing agent include amine-based compounds, acid anhydrides, active esters, carboxylic acid-based compounds, and sulfonic acid-based 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 compound (eg, triethylbenzylammonium chloride, etc.), blocked isocyanate compound (eg, dimethylamine, etc.), imidazole derivative bicyclic amidine compound and its salt (eg, imidazole, 2). -Methyl imidazole, 2-ethyl imidazole, 2-ethyl-4-methyl imidazole, 2-phenyl imidazole, 4-phenyl imidazole, 1-cyanoethyl-2-phenyl imidazole, 1- (2-cyanoethyl) -2-ethyl-4 -Methylimidazole, etc.), phosphorus compounds (eg, triphenylphosphine, etc.), S-triazine derivatives (eg, 2,4-diamino-6-methacryloyloxyethyl-S-triazine, 2-vinyl-2,4-diamino- Examples thereof include 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 agent can be used alone or in combination of two or more.

The content of the curing agent is preferably 0.01 to 15 parts by mass with respect to 100 parts by mass of the thermosetting compound (H).

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

The thiol-based chain transfer agent (I) is preferably a polyfunctional thiol having two or more thiol groups (SH groups). It is more preferable that the thiol-based chain transfer agent has 4 or more SH groups. As the number of functional groups increases, photocuring from the surface of the film to the deepest part becomes easier.

Polyfunctional thiols include, for example, hexanedithiol, decandithiol, 1,4-butandio-rubistiopropionate, 1,4-butandio-rubistioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate. , Trimethylol Propane Tristhioglycolate, Trimethylol Propane Tristhiopropionate, Trimethylol Propanetris (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 thereof include s-triazine, and preferred examples include ethylene glycol bisthiopropionate, trimethylolpropanetristhiopropionate, and pentaerythritol tetrakisthiopropionate.

The thiol-based chain transfer agent (I) can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent (I) is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the light sensitivity is improved and wrinkles are less likely to occur on the pattern surface.

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

The polymerization inhibitor (J) is, for example, catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatecol, 3-ethylcatechol, 4-ethylcatechol. , 2-propyl catechol, 3-propyl catechol, 4-propyl catechol, 2-n-butyl catechol, 3-n-butyl catechol, 4-n-butyl catechol, 2-t-butyl catechol, 3-t-butyl catechol , 4-t-butylcatechol, alkylcatechol compounds such as 3,5-di-t-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorsinol, 4-ethylresorsinol, 2 -Alkylresolsinol compounds such as propylresorsinol, 4-propylresorsinol, 2-n-butylresorsinol, 4-n-butylresorsinol, 2-t-butylresorsinol, 4-t-butylresorsinol, etc. Alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine. Examples thereof include phosphin compounds such as phosphine compounds such as trioctylphosphinoxide and phosphinoxide compounds such as triphenylphosphine oxide, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol and fluoroglucolcin.

The content of the polymerization inhibitor (J) is preferably 0.01 to 0.4% by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition.

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

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

Benzotriazole compounds include, for example, 2- (5-methyl-2-hydroxyphenyl) benzotriazole, 2- (2-hydroxy-5-t-butylphenyl) -2H-benzotriazole, 2- [2-hydroxy-3. , 5-bis (α, α-dimethylbenzyl) phenyl] -2H-benzotriazole, 2- (3-t butyl-5-methyl-2-hydroxyphenyl) -5-chlorobenzotriazole, 2- (2'- Hydroxy-5'-t-octylphenyl) benzotriazole, 5% 2-methoxy-1-methylethylacetate and 95% benzenepropanoic acid, 3- (2H-benzotriazole 2-yl)-(1,1- A mixture of dimethylethyl) -4-hydroxy, C7-9 side chains and linear alkyl esters, 2- (2H-benzotriazole 2-yl) -4,6-bis (1-methyl-1-phenylethyl) phenol, 2- (2H-benzotriazole 2-yl) -6- (1-methyl-1-phenylethyl) -4- (1,1,3,3-tetramethylbutyl) phenol, methyl 3- (3- (2H) -Reaction product of -benzotriazole 2-yl) -5-t-butyl-4-hydroxyphenyl) propionate / polyethylene glycol 300, 2- (2H-benzotriazole 2-yl) -4- (1,1,3) 3-Tetramethylbutyl) phenol, 2,2'-methylenebis [6- (2H-benzotriazole2-yl) -4- (1,1,3,3-tetramethylbutyl) phenol], 2- (2H- Benzotriazole 2-yl) -p-cresol, 2- (5-chloro-2H-benzotriazole 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-benzotriazole2-yl) phenyl] propionate, 2-ethylhexyl-3- [3-tert-butyl-4-hydroxy-5- (5-chloro-2H-benzotriazole2-yl) ) Phenyl] propionate can be mentioned.

Commercially available products include, for example, TINUVIN P, PS, 234,326,329,384-2,900, 928,99-2,1130 manufactured by BASF Japan, and ADEKA STUB LA-29, LA-31RG, LA manufactured by ADEKA. -23, LA-36, KEMISORB71, 73, 74, 79, 279 manufactured by Chemipro Kasei Co., Ltd., RUVA-93 manufactured by Otsuka Chemical Co., Ltd., and the like.

The triazine compound is, for example, 2,4-bis (2,4-dimethylphenyl) -6- (2-hydroxy-4-n-octyloxyphenyl) -1,3,5-triazine, 2- [4. 6-bis (2,4-dimethylphenyl) -1,3,5-triazine-2-yl] -5- [3- (dodecyloxy) -2-hydroxypropoxy] phenol, 2- (2,4-dihydroxy) Phenyl) -4,6-bis (2,4-dimethylphenyl) -1,3,5-triazine and (2-ethylhexyl) -glycidate ester reaction product, 2,4-bis "2-hydroxy-4 -Butoxyphenyl "-6- (2,4-dibutoxyphenyl) -1,3,5-triazine, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5-( Hexyloxy) Phenol, 2- (4,6-diphenyl-1,3,5-triazine-2-yl) -5- [2- (2-ethylhexanoyloxy) ethoxy] phenol, 2,4,6- Examples thereof include tris (2-hydroxy-4-hexyloxy-3-methylphenyl) -1,3,5-triazine.

Commercially available products include, for example, KEMISORB102 manufactured by Chemipro Kasei Co., Ltd., TINUVIN400, 405,460,477,479,1577ED manufactured by BASF Japan, ADEKA STAB LA-46, LA-F70 manufactured by ADEKA, and CYASORB UV-manufactured by Sun Chemical Co., Ltd. 1164 and the like can be mentioned.

Benzophenone compounds include, for example, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone 5-sulfonic acid-3 water temperature, 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-octadesiloxy Examples thereof include benzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2', 4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like.

Examples of commercially available products include KEMISORB10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., SEESORB 101, 107 manufactured by Sipro Kasei Co., Ltd., ADEKA STAB 1413 manufactured by ADEKA Co., Ltd., UV-12 manufactured by Sun Chemical Co., Ltd. and the like.

Examples of the salicylic acid ester-based compound include phenyl salicylate, p-octylphenyl salicylate, and p-tert-butyl phenyl salicylate.

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

[Antioxidant (L)]
The photosensitive coloring composition of the present invention may contain an antioxidant (L). As the antioxidant (L), the photopolymerization initiator (D) and the thermosetting compound (I) contained in the photosensitive coloring composition undergo yellowing due to oxidation due to heat curing or a thermal process during ITO annealing. prevent. In particular, when the concentration of the colorant (A) in the photosensitive coloring composition is high, the content of the polymerizable compound (C) is relatively reduced, so that the amount of the photopolymerization initiator (D) is increased or the thermosetting compound is used. The cured film tends to turn yellow when the formulation of (I) is applied. Therefore, by containing an antioxidant, yellowing of the cured film due to oxidation during the heating step is prevented.

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

Among these, a hydride-based phenol-based antioxidant, a hydride-based amine-based antioxidant, a phosphorus-based antioxidant, and a sulfur-based antioxidant are preferable.

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) -trion, 1,1,3-tris- (2'-methyl-4'-hydroxy-5'-t-butylphenyl) -butane, 4,4'-butylidene-bis- (2- t-butyl-5-methylphenol), 3- (3,5-di-t-butyl-4-hydroxyphenyl) stearyl propionate, pentaerythritol tetrakis [3- (3,5-di-t-butyl-4) -Hydroxyphenyl) propionate, 3,9-bis [2- [3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl] -2,4,8 , 10-Tetraoxaspiro [5.5] undecane, 1,3,5-tris (3,5-di-t-butyl-4-hydroxyphenylmethyl) -2,4,6-trimethylbenzene, 1,3 , 5-Tris (3-hydroxy-4-t-butyl-2,6-dimethylbenzyl) -1,3,5-triazine-2,4,6 (1H, 3H, 5H) -trione, 2,2' -Methylenebis (6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis- (3,5-di-t-butyl-4-hydroxyphenyl) -propionate, N, N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 4,6-bis (Dodecylthiomethyl) -o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis (octylthiomethyl) -o-cresol, bis [ 3- (3-Methyl-4-hydroxy-5-t-butylphenyl) propionic acid] ethylenebisoxybisethylene, 1,6-hexanediolbis [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, etc. Can be mentioned.

Commercially available products include, for example, ADEKA tabs AO-20, AO-30, AO-40, AO-50, AO-60, AO-80, AO-330 manufactured by ADEKA, and KEMINOX 101, 179, 76, 9425 manufactured by Chemipro. , BASF Japan's IRGANOX 1010, 1035, 1076, 1098, 1135, 1330, 1726, 1425WL, 1520L, 245, 259, 3114, 5057, 565, Sun Chemical's Sianox CY-1790, CY-2777, etc. Can be mentioned.

Hindered amine antioxidants include, for example, 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-tetramethylpiperidine-4-yl) carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate , 2,2,6,6-Tetramethyl-4-piperidylmethacrylate, 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-piperidinethanol 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-diazadecan-1,10-diamine, bisdecanediate (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, reaction product of 1,1-dimethylethylhydroperoxide and octane, bis (1,2,2,6,6-pentamethyl-4-piperidyl) [[3,5-bis (1,5-bis) 1 dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate methyl 1,2,2,6,6-pentamethyl-4-piperidylsevakate, 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-Hexamethylenediamine, 2-methyl-2- (2,2,6,6-tetramethyl-4-piperidyl) amino-N- (2,2,6,6-tetramethyl-4-piperidyl) propionamide And so on.

Commercially available products include, for example, ADEKA's 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, Tinuvin111FDL, 123, 144, 249, 292, 5100 manufactured by BASF Japan, Siasorb UV-3346 manufactured by Sun Chemical Co., Ltd. , UV-3259, UV-3853 and the like.

Phylline antioxidants include, for example, di (2,6-di-t-butyl-4-methylphenyl) pentaerythritol diphosphite, distearyl pentaerythritol diphosphite, 2,2'-methylenebis (4,6). -Di-t-butylphenyl) 2-ethylhexyl phosphite, tris (2,4-di-t-butylphenyl) phosphite, tris (nonylphenyl) phosphite, tetra (C12-C15 alkyl) -4,4' -Isopropyridene diphenyl diphosphite, diphenylmono (2-ethylhexyl) phosphite, diphenylisodecylphosphite, tris (isodecyl) phosphite, triphenylphosphite, tetrakis (2,4-di-t-butylphenyl)- 4,4-Biphenyldiphoshonito, Tris (tridecyl) phosphite, phenylisooctylphosphite, phenylisodecylphosphite, phenyldi (tridecyl) phosphite, diphenylisooctylphosphite, diphenyltridecylphosphite, 4,4 '-Isopropyridene 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) butanetriphosphite, 3,5-di-t-butyl-4-hydroxybenzylphosphite diethyl ester, sodiumbis (4-t-butylphenyl) phos Fight, Sodium-2,2-Methylene-bis (4,6-di-t-butylphenyl) -phosphite, 1,3-bis (diphenoxyphosphonyloxy) -benzene, ethylbis phosphite (2,4) -Dit-butyl-6-methylphenyl) and the like.

Commercially available products include, for example, ADEKA tab PEP-36, PEP-8, HP-10, 211, 1178, 1500, C, 135A, 3010, TPP, IRGAFOS168 manufactured by BASF Japan, and HostanoxP manufactured by Clariant Chemicals. -EPQ and the like can be mentioned.

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- Cresol, 2,4-bis [(laurylthio) methyl] -o-cresol and the like can be mentioned.

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

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

The content of the antioxidant (L) is preferably 0.5 to 5.0% by mass based on 100% by mass of the non-volatile content of the photosensitive coloring composition. When an appropriate amount is contained, the transmittance, spectral characteristics, and sensitivity are improved.

[Leveling agent (M)]
The photosensitive coloring composition of the present invention can contain a leveling agent (M). As a result, the wettability and dryness to the substrate at the time of coating are further improved. Examples of the leveling agent (M) include silicon-based surfactants, fluorine-based surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, amphoteric surfactants and the like.

Examples of the silicon-based surfactant include a linear polymer composed of a siloxane bond and a modified siloxane polymer having an organic group introduced into a side chain or a terminal.

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 Big Chemie. 378,3455, UV3510,3570, FZ-7002, 2110, 2122, 2123, 2191, 5609, manufactured by Toray Industries, Inc., X-22-4952, X-22-4272, X-, manufactured by Shin-Etsu Chemical Co., Ltd. Examples thereof include 22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341 and the like.

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

Commercially available products include, for example, AGC Seimi Chemical's Surflon S-242,243,420,611,651,386 and DIC's Megafuck F-253,477,551,552,555,558,560,570. , 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 Electronics. , EF-PP32C1, Neos Co., Ltd. Futergent 602A and the like.

Nonionic surfactants include, for example, polyoxyethylene lauryl ether, polyoxyethylene cetyl ether, polyoxyethylene stearyl ether, polyoxyethylene oleyl ether, polyoxyethylene alkyl ether, polyoxyethylene myristel ether, and polyoxyethylene octyl. Dodecyl ether, polyoxyalkylene alkyl ether, polyoxyphenylenedistyrene phenyl ether, polyoxyethylene tribenzylphenyl ether, polyoxyethylene polyoxypropylene glycol, polyoxyalkylene alkenyl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene Alkyl ether phosphate ester, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan distearate, sorbitan tristearate, sorbitan monoolate, sorbitan triolate, sorbitan sesquiolate, polyoxyethylene sorbitan mono Laurate, Polyoxyethylene sorbitan monopalmitate, Polyoxyethylene sorbitan monostearate, Polyoxyethylene sorbitan tristearate, Polyoxyethylene sorbitan monoolate, Polyoxyethylene sorbitan triisostearate, Polyoxytetraoleate Ethylene sorbit, glycerol monostearate, glycerol monooleate, polyethylene glycol monolaurate, polyethylene glycol monostearate, polyethylene glycol distearate, polyethylene glycol monostearate, polyoxyethylene hydrogenated castor oil, polyoxyethylene alkylamine, alkyl Examples thereof include alkanolamide and alkylimidazolin.

Commercially available products include, for example, Emargen 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, Latemul PD-420, PD-430, PD-430S, PD-450, Leodor SP-L10, SP-P10, SP-S10V, SP-S20, SP-S30V, SP-O10V , SP-O30V, Super SP-L10, AS-10V, AO-10V, AO-15V, TW-L120, TW-L106, TW-P120, TW-S120V, TW-S320V, TW-O120V, TW-O106V, TW-IS399C, Super TW-L120, 430V, 440V, 460V, MS-50, MS-60, MO-60, MS-165V, Emanon 1112, 3199V, 3299V, 3299RV, 4110, CH-25, CH-40, CH-60 (K), Polymer 102, 105, 105A, 302, 320, Aminone PK-02S, L-02, Homogenol L-95, ADEKA Adecapluronic® 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 and the like can be mentioned.

Examples of the cationic surfactant include alkylquaternary ammonium salts such as alkylamine salts, lauryltrimethylammonium chlorides, stearyltrimethylammonium chlorides, and cetyltrimethylammonium chlorides, and ethylene oxide adducts thereof.

Examples of commercially available products include acetamine 24, coatamine 24P, 60W, 86P conch piercing manufactured by Kao Corporation.

Anionic surfactants include, for example, polyoxyethylene alkyl ether sulfate, sodium dodecylbenzene sulfonate, alkali salt of styrene-acrylic acid copolymer, sodium alkylnaphthalene sulfonate, sodium alkyldiphenyl ether disulfonate, monoethanol lauryl sulfate. Examples thereof include amines, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine of styrene-acrylic acid copolymer, polyoxyethylene alkyl ether phosphate and the like.

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

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 alkylamine oxides such as lauryldimethylamine oxide.

Examples of commercially available products include Anhitor 20AB, 20BS, 24B, 55AB, 86B, 20Y-B, 20N manufactured by Kao Corporation.

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

The content of the leveling agent (M) is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. Within this range, the balance between the coatability and the adhesiveness of the photosensitive coloring composition is further improved.

[Storage stabilizer (N)]
The photosensitive coloring composition of the present invention can contain a storage stabilizer (N). This stabilizes the viscosity of the photosensitive coloring composition over time. The storage stabilizer (N) includes, for example, quaternary ammonium chloride such as benzyltrimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and phosphoric acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, tetraphenyl and the like. Examples thereof include organic phosphine and phosphite.

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

[Adhesion improver (O)]
The photosensitive coloring composition of the present invention can contain an adhesion improver (O). This improves the adhesion between the cured film and the base material. In addition, the photolithography method facilitates the formation of narrow patterns.

Examples of the adhesion improver (O) include a silane coupling agent and the like. Examples of the silane coupling agent include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, and 3-methacryloxypropylmethyldiethoxysilane. (Meta) acrylic silanes such as 3-methacryloxypropyltriethoxysilane, 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 dimethyl-butylidene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N- (vinylbenzyl) -2-aminoethyl-3-aminopropyltrimethoxysilane hydrochloride, 3-mercaptopropyl Melcaptos such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane, styryls such as p-styryltrimethoxysilane, ureids such as 3-ureidopropyltriethoxysilane, bis (triethoxysilylpropyl) tetrasulfide and the like. Examples thereof include silane coupling agents such as sulfides and isocyanates such as 3-isocyanuspropyltriethoxysilane.

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

The content of the adhesion improver (O) is preferably 0.01 to 10 parts by mass, more preferably 0.05 to 5 parts by mass with respect to 100 parts by mass of the colorant (A).

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

The organic solvent (P) is, for example, 1,2,3-trichloropropane, 1-methoxy-2-propanol, ethyl lactate, 1,3-butanjiol, 1,3-butylene glycol, 1,3-butylene glycol. Diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexene-1-one, 3,3,5-trimethylcyclohexanone , 3-ethoxypropionate ethyl, 3-methyl-1,3-butanjiol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutylacetate, 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-propylacetate, N -Methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, Isophoron, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monoterriary 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 acethe G, 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 Examples thereof include alcohol, methylisobutylketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid ester and the like. Among these, from the viewpoint of dispersibility of pigments and solubility of alkali-soluble resins, ethyl lactate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate and the like Alcohols such as glycol acetates, benzyl alcohols and diacetone alcohols and ketones such as cyclohexanone are preferable.

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

[Manufacturing method of photosensitive coloring composition]
The photosensitive coloring composition of the present invention is subjected to a dispersion treatment by adding, for example, a colorant (A), an alkali-soluble resin (B), a dispersion resin (G), a dye derivative (F), an organic solvent (P) and the like. By doing so, a dispersion is produced. Then, it can be produced by blending the polymerizable compound (C), the photopolymerization initiator (D) and the like with the dispersion and mixing them. The timing of blending each material is arbitrary. Further, the dispersion step can be performed a plurality of times.

Examples of the disperser for performing the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annual 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 having high dispersion stability.

As a method for measuring the average dispersed particle size (secondary particle size), for example, Nikkiso's Microtrack UPA-EX150, which employs a dynamic light scattering method (FFT power-spector method), is used to absorb particle permeability. The particle shape is non-spherical, and the D50 particle diameter is the average diameter. As the diluting solvent for measurement, the organic solvent used for dispersion is used, and it is preferable to measure the sample treated by ultrasonic waves immediately after sample preparation because it is easy to obtain results with little variation.

The photosensitive coloring composition is prepared by means such as centrifugation, filtration with a sintering filter or a membrane filter, and coarse particles of 5 μm or more, preferably coarse particles of 1 μm or more, more preferably 0.5 μm or more, and coarse particles of 0.5 μm or more. It is preferable to remove the mixed dust. The photosensitive coloring composition of the present invention preferably contains substantially no particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

<Color filter>
The color filter of the present invention comprises a substrate and a filter segment formed from the photosensitive coloring composition of the present invention. The color filter segment preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of the colorant (A) to be used. Further, the color filter may have a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment in place of or in addition to the color filter segment.
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 that uses an aluminum electrode or a metal thin film as a reflective surface.

[Manufacturing method of color filter]
The color filter manufacturing method is not particularly limited, and for example, a step of applying a photosensitive coloring composition on a substrate to form a layer of the composition (1), and a step of exposing the layer in a pattern through a mask. It can be produced by performing (2), a step (3) of alkali-development of an unexposed portion to form a patterned cured film, and a step (4) of heat-treating (post-baking) the pattern.

Hereinafter, a method for manufacturing a color filter will be described in detail.
(Step (1))
In the step (1) of forming the layer of the composition, the photosensitive coloring composition is applied onto the substrate by, for example, rotary coating, roll coating, slit coating, cast coating, or inkjet coating. If necessary, dry (pre-bake) at a temperature of 50 to 120 ° C. for 10 to 120 seconds using an oven, a hot plate, or the like.
Examples of the substrate include a glass substrate and a silicon substrate. For example, an image pickup element such as a CCD or CMOS may be formed on the surface of the silicon substrate. Further, if necessary, an undercoat layer may be provided on the substrate for improving the adhesion with the layer from the upper part, preventing the diffusion of substances, and flattening the surface of the substrate.
The film thickness of the layer is preferably 0.05 to 10.0 μm after drying, and more preferably 0.3 to 5 μm.

(Step (2))
In the exposure step, the layer obtained in the step (1) is exposed to a specific pattern via a mask using, for example, an exposure device such as a stepper. This gives a cured film.
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 the step (2) is subjected to an alkaline development treatment, so that the layer of the composition in the unexposed portion is eluted in the alkaline aqueous solution, and only the cured portion remains to obtain a patterned cured film.
The developing solution is, for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, diethylamine, dimethylethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, choline, etc. Alkaline compounds such as pyrrol, piperidine, 1,8-diazabicyclo- [5.4.0] -7-undecene and the like can be mentioned.
The concentration of the developer is preferably 0.001 to 10% by mass, more preferably 0.01 to 1% by mass.
The pH of the alkaline developer is preferably 11 to 13, more preferably 11.5 to 12.5. When used at an appropriate pH, roughening and peeling of the pattern are suppressed, and the residual film ratio after development is improved.

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

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

<Image display device>
The image display device of the present invention includes the color filter of the present invention.
The form used for the image display device is not particularly limited as long as it functions as an image display device. For example, the configuration described in "Next Generation Liquid Crystal Display Technology (written by Tatsuo Uchida, Kogyo Chosakai Co., Ltd., published in 1994)" can be mentioned.
For details on the definition of image display devices and the details of each image display device, see, for example, "Electronic Display Device (written by Akio Sasaki, Kogyo Chosakai Co., Ltd., published in 1990)", "Display Device (written by Junaki Ibuki, Industrial Books)". Co., Ltd., issued in 1989) ”.

<Solid image sensor>
The solid-state image sensor of the present invention includes the color filter of the present invention.
The form used for the solid-state image sensor is not particularly limited, but for example, a transfer composed of a plurality of photodiodes constituting a light-receiving area of the solid-state image sensor (CDCD image sensor, CMOS image sensor, etc.) and polysilicon on a substrate is used. It has an electrode, has a light-shielding film with only the light-receiving part of the photodiode open on the photodiode and the transfer electrode, and is made of silicon nitride or the like formed on the light-shielding film so as to cover the entire surface of the light-shielding film and the light-receiving part of the photodiode. It has a device protective film and has a color filter on the device protective film. Further, a configuration having a light-collecting means (for example, a microlens or the like; the same applies hereinafter) on the device protective film under the color filter (the side closer to the base material), a configuration having a light-collecting means on the color filter, and the like. May be. Further, the color filter may have a structure in which a cured film forming each colored pixel is embedded in a space partitioned by a partition wall, for example, in a grid pattern. The partition wall in this case preferably has a low refractive index for each colored pixel.
The image pickup device provided with the solid-state image pickup device of the present invention can be used not only for digital cameras and electronic devices having an image pickup function (mobile phones, smartphones, etc.), but also for in-vehicle cameras and surveillance cameras.

Hereinafter, the present invention will be described in more detail with reference to Examples. However, the present invention is not limited to these. In addition, "part" is "mass part", and "%" is "mass%".
Further, in the present invention, the non-volatile component or the non-volatile component concentration refers to the mass residue after standing in the oven at 280 ° C. for 30 minutes.

Prior to the embodiment, each measurement method will be described.

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

(Average molecular weight of alkali-soluble resin and dispersed resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the alkali-soluble and dispersed resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. Using HLC-8220GPC (manufactured by Tosoh Co., Ltd.) as an apparatus, two separation columns are connected in series, and "TSK-GEL SUPER HZM-N" is connected in two for both fillers, and the oven temperature is 40 ° C. , Tetrahydrofuran (THF) solution was used as an eluent, and the measurement was performed at a flow rate of 0.35 ml / min. The sample was dissolved in a solvent consisting of 1% by mass of the above eluent and injected with 20 microliters. The average molecular weight is a polystyrene-equivalent value.

(Acid value of alkali-soluble resin and dispersed resin)
80 ml of acetone and 10 ml of water are added to 0.5 to 1 g of an alkali-soluble resin and a dispersed resin solution, and the mixture is stirred to uniformly dissolve the solution. -555 ”manufactured by Hiranuma Sangyo Co., Ltd.) was used for titration, and the acid value (mgKOH / g) was measured. Then, the acid value per non-volatile component of the resin was calculated from the acid value of the resin solution and the non-volatile content concentration of the resin solution.

(Amine value of dispersed resin)
The amine value of the dispersed resin is a value obtained by converting the measured total amine value (mgKOH / g) into a non-volatile content according to the method of ASTM D 2074.

<Manufacturing of colorant (A)>
(Miniaturized red pigment (A-1))
C. I. 100 parts of Pigment Red 254, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. Next, the kneaded mixture was put into warm water, stirred for 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. Finely divided red pigment (A-1) was obtained by pulverization.

(Miniaturized red pigment (A-2))
C. I. 100 parts of Pigment Red 177, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60 ° C. for 6 hours. Next, the kneaded mixture was put into warm water, stirred for 1 hour while heating at about 80 ° C. to form a slurry, filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours. Finely divided red pigment (A-2) was obtained by pulverization.

(Miniaturized blue pigment (A-3))
C. I. Pigment Blue 15: 6 was charged in 100 parts, sodium chloride in 1,000 parts, and diethylene glycol in 100 parts in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), and kneaded at 50 ° C. for 12 hours. This mixture is poured into 3,000 parts of warm water, stirred with a high speed mixer for about 1 hour while heating at about 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove salt and solvent, and then at 80 ° C. The mixture was dried for 24 hours to obtain a finely divided blue pigment (A-3).

(Miniaturized purple pigment (A-4))
C. I. 100 parts of Pigment Violet 23, 1,200 parts of sodium chloride, and 100 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. Next, this kneaded product was put into 8,000 parts of warm water, stirred for 2 hours while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then 85 ° C. The mixture was dried for 24 hours to obtain a finely divided purple pigment (A-4).

(Miniaturized green pigment (A-5))
C. I. 100 parts of Pigment Green 58, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70 ° C. for 6 hours. This kneaded product is put into 3000 parts of warm water, stirred for 1 hour while heating at 70 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours and finely. A green pigment (A-5) was obtained.

(Miniaturized yellow pigment (A-6))
C. I. 100 parts of Pigment Yellow 150, 700 parts of sodium chloride, and 180 parts of diethylene glycol were charged in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 80 ° C. for 6 hours. This mixture is poured into 2,000 parts of warm water, stirred for 1 hour while heating at 80 ° C. to form a slurry, filtered and washed with water repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80 ° C. for 24 hours and finely. A solubilized yellow pigment (A-6) was obtained.

<Manufacturing of alkali-soluble resin (B)>
(Alkali-soluble resin (B-1) solution)
100 parts of cyclohexanone was charged in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. 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 Toa Synthetic Co., Ltd.) , 2, 2'-Azobisisobutyronitrile 1.1 parts mixture was added dropwise over 2 hours. After completion of the dropping, the reaction was continued for another 3 hours to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. Propylene glycol monomethyl is prepared so that the non-volatile content is 20% by mass in the previously synthesized resin solution. An alkali-soluble resin (B-1) solution was prepared by adding ether acetate (hereinafter, PGMAc). The weight average molecular weight (Mw) was 26,000.

(Alkali-soluble resin (B-2) solution)
100 parts of cyclohexanone was charged in a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube and a stirrer in a separable 4-neck flask, the temperature was raised to 80 ° C., the inside of the reaction vessel was replaced with nitrogen, and then dropped. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toa Synthetic 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 completion of the dropping, the reaction was continued for another 3 hours to obtain a copolymer resin solution. Next, for the entire amount of the obtained copolymer solution, nitrogen gas was stopped, dry air was injected for 1 hour, and the mixture was stirred, cooled to room temperature, and then 2-methacryloyloxyethyl isocyanate (Showa Denko's Karenz). A mixture of 6.5 parts of MOI), 0.08 part of dibutyltin laurate and 26 parts of cyclohexanone was added dropwise at 70 ° C. over 3 hours. After completion of the dropping, the reaction was continued for another 1 hour to obtain a solution of acrylic resin. After cooling to room temperature, about 2 parts of the resin solution is sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and cyclohexanone is added to the previously synthesized resin solution so that the non-volatile content is 20% by mass. To prepare an alkali-soluble resin (B-2) solution. The weight average molecular weight (Mw) was 18,000.

(Alkali-soluble resin (B-3) solution)
200 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 stirrer, the temperature was raised to 80 ° C. 18 parts of Milphenol Ethylene Oxide Modified Acrylate (Aronix M110 manufactured by Toa Synthetic Co., Ltd.), 10 parts of benzyl methacrylate, 18.2 parts of glycidyl methacrylate, 25 parts of methyl methacrylate, and 2,2'-azobisisobutyronitrile 2.0. The mixture of parts was added dropwise over 2 hours. After the dropping, the reaction was further carried out at 100 ° C. for 3 hours, then 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 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 9.3 parts of acrylic acid (100% of glycidyl group) in the above container, and 6 at 120 ° C. The reaction was continued for a long time, and when the non-volatile acid value reached 0.5, the reaction was terminated to obtain a solution of acrylic resin. Further, 19.5 parts of tetrahydrophthalic anhydride (100% of the generated hydroxyl group) and 0.5 part of triethylamine were subsequently added and reacted at 120 ° C. for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled, heated and dried at 180 ° C. for 20 minutes to measure the non-volatile content, and PGM Ac was added to the previously synthesized resin solution so that the non-volatile content was 20% by mass. Prepared an alkali-soluble resin (B-3) solution. The weight average molecular weight (Mw) was 19,000.

(Alkali-soluble resin (B-4) solution)
A separable flask with a cooling tube was prepared as a reaction tank, while 40 parts of dimethyl-2,2'-[oxybis (methylene)] bis-2-propenoate, 40 parts of methacrylic acid, and methacrylic acid were prepared as a monomer dropping tank. Prepare a well-stirred mixture of 120 parts of methyl, 4 parts of t-butylperoxy2-ethylhexanoate (“Perbutyl O” manufactured by Nippon Oil & Fats), and 40 parts of PGMAc, and use an n-dodecanethiol as a chain transfer agent dropping tank. Eight parts and 32 parts of PGMAc were well mixed and mixed.
After charging 200 parts of PGMAc into the reaction vessel and substituting with nitrogen, the temperature of the reaction vessel was raised to 90 ° C. by heating with an oil bath while stirring. After the temperature of the reaction tank became stable at 90 ° C., dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. The dropping was carried out over 135 minutes while keeping the temperature at 90 ° C. 60 minutes after the dropping was completed, the temperature was raised to 110 ° C. After maintaining 110 ° C. for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of the oxygen / nitrogen = 5/95 (volume ratio) mixed gas 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 charged in the reaction vessel, and the mixture was allowed to react at 110 ° C. for 12 hours. rice field. After that, 150 parts of PGMAc is added and cooled to room temperature, about 2 g of the resin solution is sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content, and the non-volatile content becomes 20% by mass in the previously synthesized resin solution. As described above, PGMAc was added to obtain an alkali-soluble resin (B-4) solution. The weight average molecular weight was 18,000.

(Alkali-soluble resin (B-5) solution)
Introduce 150 parts of PGMAc into a flask equipped with a stirrer, thermometer, reflux cooling tube, dropping rotor and nitrogen introduction tube, change the atmosphere inside the flask from air to nitrogen, raise the temperature to 100 ° C, and then benzyl methacrylate. Azobisiso in a mixture consisting of 70.5 parts (0.40 mol), 71.1 parts (0.50 mol) of glycidyl methacrylate, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 164 parts of PGMAc. The solution to which 3.6 parts of butyronitrile was added was added dropwise to the flask over 2 hours from the dropping rotor, and stirring was continued 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, (100 mol% with respect to the glycidyl group of glycidyl methacrylate used in this reaction)], trisdimethylaminomethylphenol 0. 9. 9 parts and 0.145 parts of hydroquinone were put into a flask, and the reaction was continued at 110 ° C. for 6 hours, and the reaction was terminated when the non-volatile 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 photosensitive transparent resin solution having an acid value of 80 mgKOH / g. .. After cooling to room temperature, about 2 parts of the photosensitive transparent resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. PGMAc was added so as to prepare an alkali-soluble resin (B-5) solution. The mass average molecular weight (Mw) was 12,000.

(Alkali-soluble resin (B-6) solution)
Introduce 150 parts of PGMAc into a flask equipped with a stirrer, thermometer, reflux cooling tube, dropping rotor and nitrogen introduction tube, change the atmosphere inside the flask from air to nitrogen, raise the temperature to 100 ° C, and then benzyl methacrylate. Azobisisobuty in a mixture consisting of 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 136 parts of PGMAc. The solution to which 3.6 parts of nitrogen was added was added dropwise from the dropping rotor 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 35.5 parts of glycidyl methacrylate [0.25 mol, (50 mol% with respect to the carboxyl group of methacrylic acid used in this reaction)], trisdimethylaminomethylphenol 0. 9. 9 parts and 0.145 parts of hydroquinone were put into a flask, and the reaction was continued at 110 ° C. for 6 hours to obtain a photosensitive transparent resin solution having an acid value of 79 mgKOH / g. After cooling to room temperature, about 2 parts of the photosensitive transparent resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the non-volatile content. PGMAc was added so as to prepare an alkali-soluble resin (B-6) solution. The mass average molecular weight (Mw) was 13,000.

<Manufacturing of acid group-containing aromatic urethane (meth) acrylate (C1)>
(Acid group-containing aromatic urethane acrylate (C1-1) solution)
In a 5-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, and a dropping tube, 400 parts of 2-hydroxy-3-acryloyloxypropylmethacrylate, 100 parts of PGMAc, N, N-dimethylbenzylamine 0. Five parts were charged, the temperature was raised to 70 ° C., and a mixture of 162 parts of toluene diisocyanate and 162 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropping, the reaction was carried out at a temperature of 50 to 70 ° C. for 8 hours, and the disappearance of absorption of isocyanate of 2180 cm ^-1 was confirmed by IR. Then, 85 parts of mercaptoacetic acid and 0.4 part of 4-methoxyphenol were charged and reacted at a temperature of 50 to 60 ° C. for 6 hours. The non-volatile content was adjusted to 50% by mass to obtain an acid group-containing aromatic urethane acrylate (C1-1) solution having an average polymerizable unsaturated group number of 3.

(Acid group-containing aromatic urethane acrylate (C1-2) solution)
400 parts of pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 part of N, N-dimethylbenzylamine were placed in a 5-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, and a dropping tube at 70 ° C. A mixture of 116 parts of toluene diisocyanate and 116 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropping, the reaction was carried out at a temperature of 50 to 70 ° C. for 8 hours, and the disappearance of absorption of isocyanate of 2180 cm ^-1 was confirmed by IR. Then, 66 parts of mercaptoacetic acid and 0.4 parts of 4-methoxyphenol were charged and reacted at a temperature of 50 to 60 ° C. for 6 hours. The non-volatile content was adjusted to 50% by mass to obtain an acid group-containing aromatic urethane acrylate (C1-2) solution having an average polymerizable unsaturated group number of 5.

(Acid group-containing aromatic urethane acrylate (C1-3) solution)
In a 5-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, and a dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N, N-dimethylbenzylamine were charged, and 70 parts were charged. The temperature was raised to ° C., and a mixture of 66 parts of toluene diisocyanate and 66 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropping, the reaction was carried out at a temperature of 50 to 70 ° C. for 8 hours, and the disappearance of absorption of isocyanate of 2180 cm ^-1 was confirmed by IR. Then, 35 parts of mercaptoacetic acid and 0.6 part of 4-methoxyphenol were charged and reacted at a temperature of 50 to 60 ° C. for 6 hours. The non-volatile content was adjusted to 50% by mass to obtain an acid group-containing aromatic urethane acrylate (C1-3) solution having an average polymerizable unsaturated group number of 9.

<Manufacturing of aliphatic urethane (meth) acrylate (C3)>
(Liphatic urethane acrylate (C3-1) solution)
400 parts of pentaerythritol triacrylate, 100 parts of PGMAc, and 0.5 part of N, N-dimethylbenzylamine were placed in a 5-port flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, and a dropping tube at 70 ° C. A mixture of hexamethylene diisocyanate part 112 and PGMAc 112 parts was added dropwise from the dropping tube over 2 hours. After the dropping, the reaction was carried out at a temperature of 50 to 70 ° C. for 8 hours, and the disappearance of absorption of isocyanate of 2180 cm ^-1 was confirmed by IR. The non-volatile content was adjusted to 50% by mass to obtain an aliphatic urethane acrylate (C3-1) solution having a polymerizable unsaturated group number of 6.

(Liphatic urethane acrylate (C3-2) solution)
A 5-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, and a dropping tube is charged with 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N, N-dimethylbenzylamine, and 70 parts. The temperature was raised to ° C., and a mixture of 64 parts of hexamethylene diisocyanate and 64 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropping, the reaction was carried out at a temperature of 50 to 70 ° C. for 8 hours, and the disappearance of absorption of isocyanate of 2180 cm ^-1 was confirmed by IR. The non-volatile content was adjusted to 50% by mass to obtain an aliphatic urethane acrylate (C3-2) solution having 10 polymerizable unsaturated groups.

(Liphatic urethane acrylate (C3-3) solution)
A 5-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, and a dropping tube is charged with 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N, N-dimethylbenzylamine, and 70 parts. The temperature was raised to ° C., and a mixture of 64 parts of hexamethylene diisocyanate and 64 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropping, the reaction was carried out at a temperature of 50 to 70 ° C. for 8 hours, and the disappearance of absorption of isocyanate of 2180 cm ^-1 was confirmed by IR. Then, 35 parts of mercaptoacetic acid and 0.4 parts of 4-methoxyphenol were charged and reacted at a temperature of 50 to 60 ° C. for 6 hours. The non-volatile content was adjusted to 50% by mass to obtain an acid group-containing aliphatic urethane acrylate (C3-3) solution having an average polymerizable unsaturated group number of 9.

<Manufacturing of alicyclic urethane (meth) acrylate (C4)>
(Alicyclic urethane acrylate (C4-1) solution)
In a 5-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, and a dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N, N-dimethylbenzylamine were charged, and 70 parts were charged. The temperature was raised to ° C., and a mixture of isophorone diisocyanate portion 84 and PGMAc 84 portion was added dropwise from the dropping tube over 2 hours. After the dropping, the reaction was carried out at a temperature of 50 to 70 ° C. for 8 hours, and the disappearance of the absorption of isocyanate of 2180 cm ^-1 was confirmed by IR. The non-volatile content was adjusted to 50% by mass to obtain an alicyclic urethane acrylate (C4-1) solution having 10 polymerizable unsaturated groups.

<Manufacturing of other polymerizable compound (C5)>
(Aromatic urethane acrylate (C5-1) solution)
In a 5-necked flask equipped with a stirrer, a reflux condenser, a nitrogen introduction tube, a thermometer, and a dropping tube, 400 parts of dipentaerythritol pentaacrylate, 100 parts of PGMAc, and 0.5 part of N, N-dimethylbenzylamine were charged, and 70 parts were charged. The temperature was raised to ° C., and a mixture of 66 parts of toluene diisocyanate and 100 parts of PGMAc was added dropwise from the dropping tube over 2 hours. After the dropping, the reaction was carried out at a temperature of 50 to 70 ° C. for 8 hours, and the disappearance of absorption of isocyanate of 2180 cm ^-1 was confirmed by IR. PGMAc was added so that the non-volatile content was 50% by mass to obtain an aromatic urethane acrylate (C5-1) solution having 10 polymerizable unsaturated groups.

<Manufacturing of dispersed resin (G)>
(Dispersed resin (G-1) solution)
In a reaction vessel equipped with a gas introduction tube, temperature, condenser, and stirrer, 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 were charged and replaced with nitrogen gas. The inside of the reaction vessel was heated and stirred at 50 ° C., and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90 ° C., and the reaction was carried out for 7 hours while adding a solution in which 0.1 part of 2,2'-azobisisobutyronitrile was added to 90 parts of PGMAc. It was confirmed that 95% of the reaction occurred by measuring the non-volatile content. 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 were added as a catalyst, and the mixture was 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 PGMAc was added and diluted 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 (G-1) solution having a weight average molecular weight of 8,500 was obtained.

(Dispersed resin (G-2) solution)
In a reaction vessel equipped with a gas introduction tube, a thermometer, a condenser, and a stirrer, 108 parts of 1-thioglycerol, 174 parts of pyromellitic acid anhydride, 650 parts of PGMAc, and 0.2 parts of monobutyltin oxide as a catalyst were charged with nitrogen gas. After the substitution, the reaction was carried out at 120 ° C. for 5 hours (first step). By measuring the acid value, it was confirmed that 95% or more of the acid anhydride was half-esterified. Next, 160 parts of the compound obtained in the first step, 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 in terms of non-volatile content. 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 reaction was carried out for 12 hours. (Second step). It was confirmed that 95% of the reaction occurred by measuring the non-volatile content. 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 by IR. The reaction was carried out until the disappearance of the peak of -1 was confirmed (third step). After confirming the disappearance of the peak, the reaction solution was cooled and the non-volatile content was adjusted with PGMAc to obtain a dispersed resin (G-2) solution having a non-volatile content of 30%. The acid value of the obtained dispersed resin (G-2) was 68 mgKOH / g, the unsaturated double bond equivalent was 1,593, and the weight average molecular weight was 13,000.

(Dispersed resin (G-3) solution)
A reactor equipped with a gas introduction tube, a condenser, a stirring blade, and a thermometer was charged with 30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine, and nitrogen was poured. While stirring at 50 ° C. for 1 hour, the inside of the system was replaced with nitrogen. Next, 9.3 parts of ethyl bromoisobutyrate, 5.6 parts of cuprous chloride, and 133 parts of PGMAc were charged, and the temperature was raised to 110 ° C. under a nitrogen stream to start the polymerization of the first block (B block). After polymerization for 4 hours, the polymerization solution was sampled and the non-volatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more in terms of the non-volatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidylmethacrylate (manufactured by Hitachi Kasei Kogyo Co., Ltd., Funkryl FA-711MM) as a second block (A block) monomer were added to this reactor. The mixture was charged and stirred while maintaining the atmosphere of 110 ° C. and nitrogen, and the reaction was continued. Two hours after the addition of 1,2,2,6,6-pentamethylpiperidylmethacrylate, the polymerization solution was sampled and the non-volatile content was measured, and the polymerization conversion rate of the second block (A block) was 98 when converted from the non-volatile content. % Or more, and the reaction solution was cooled to room temperature to terminate the polymerization. PGMAc was added and diluted so that the non-volatile content was 30% in the non-volatile content measurement to obtain a dispersed resin (G-3) solution having an amine value of 57 mgKOH / g per non-volatile content and a number average molecular weight of 4,500 (Mn). ..

<Manufacturing of dispersion>
(Dispersion 1)
The following raw materials are stirred and mixed so as to be uniform, and then dispersed for 3 hours with an Eiger mill (“Mini Model M-250 MKII” manufactured by Eiger Japan Co., Ltd.) using a zirconia bead having a diameter of 0.5 mm, and then the pore diameter. The dispersion 1 was prepared by filtering with a 1.0 μm filter. The organic solvent (P-1) is PGMAc.
Finely divided red pigment (A-1): 14.0 parts Dye derivative (F-1): 1.0 part Dispersed resin (G-1) solution: 10.0 parts Dispersed resin (G-2) solution: 10 .0 parts Organic solvent (P-1): 65.0 parts

Dye derivative (F-1): The following structure

Dispersions 2 to 6 were prepared in the same manner as in Dispersion 1 except that the raw materials and amounts shown in Table 1 were changed.

Dye derivative (F-2) in Table 1: The following structure

<Manufacturing of photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition 1)
The following raw materials were mixed and stirred, and filtered through a filter having a pore size of 1.0 μm to obtain a photosensitive coloring composition 1.
Dispersion 1: 17.0 parts Dispersion 2: 15.0 parts Dispersion 6: 0.3 parts Alkali-soluble resin (B) solution: 15.0 parts Acid group-containing urethane acrylate (C1-1) solution: 3. 0 part lactone-modified (meth) acrylate (C2-1): 1.5 parts Other polymerizable compound (C5-2): 2.7 parts Photopolymerization initiator (D1-2-1): 0.15 parts Epoxy compound (H1): 0.4 part Polymerization inhibitor (J): 0.01 part Leveling agent (M): 1.0 part Organic solvent (P): 43.94 parts

[Examples 2 to 40, Comparative Examples 1 to 4]
(Photosensitive coloring compositions 2-44)
Photosensitive coloring compositions 2 to 44 were prepared in the same manner as in Example 1 except that the photosensitive coloring composition 1 of Example 1 was changed to the raw materials and amounts shown in Tables 2-1 to 2-4. did.

The raw materials listed in Tables 2-1 to 2-4 are as follows.

[Alkali-soluble resin (B) solution]
Alkali-soluble resin (B-1) to (B-6) solutions were mixed in equal amounts to obtain an alkali-soluble resin (B) solution.

[Polymerizable compound (C)]
(Lactone-modified (meth) acrylate (C2))
C2-1: KAYARAD DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.)
C2-2: KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)
C2-3: KAYARAD DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.)
(Other polymerizable compound (C5))
C5-2: KAYARAD DPHA (Made by Nippon Kayaku Co., Ltd., a mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)
C5-3: Aronix M-521 (manufactured by Toagosei Co., Ltd.)

[Photopolymerization Initiator (D)]
(Oxime compound (D1))
[Oxime-based compound (D1-1) containing one oxime group in one molecule]
D1-1-1: Irgacure OXE-02 (manufactured by BASF)
[Oxime-based compound containing two oxime groups in one molecule (D2-1)]
D2-1-1: Compound represented by the above chemical formula (5) D2-1-2: Compound represented by the above chemical formula (6) (acetophenone-based compound (D2))
D2-1: Irga Cure 907 (manufactured by BASF)
D2-2: Irgacure 369 (manufactured by BASF)

[Sensitizer (E)]
(Thioxanthone compound (E1))
E1-1: 2,4-diethylthioxanthone (benzophenone compound (E2))
E2-1: 4,4'-bis (diethylamino) benzophenone

[Thermosetting compound (H)]
(Epoxy compound (H1))
H1-1: EHPE-3150 (manufactured by Daicel)
H1-2: Denacol EX611 (manufactured by Nagase Chemtex)
H1-3: Triglycidyl isocyanurate The above (H1-1) to (H1-3) were mixed in the same amount to prepare a thermosetting compound (H).

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

[Leveling agent (M)]
M-1: A solution prepared by dissolving BYK-330 (manufactured by Big Chemie) in 2 parts and PGMAc in 98 parts was used as a leveling agent (M).

[Organic solvent (P)]
P-1: Propylene glycol monomethyl ether acetate 30 parts P-2: Cyclohexanone 30 parts P-3: Ethyl 3-ethoxypropionate 10 parts P-4: Propylene glycol monomethyl ether 10 parts P-5: Cyclohexanol acetate 10 parts P -6: 10 parts or more of diproprene glycol methyl ether acetate and (P-1) to (P-6) were mixed in the above parts by mass to prepare an organic solvent (P).

<Evaluation of photosensitive coloring composition>
Regarding the obtained photosensitive coloring compositions 1 to 44 (Examples 1 to 40, Comparative Examples 1 to 4), the evaluation of water stain, pattern forming property (adhesion, shape, residual film ratio), and surface wrinkles are as follows. I went by the method of. The evaluation results are shown in Table 3.

[Water stain evaluation]
The obtained photosensitive coloring composition was coated on a glass substrate (Eagle 2000 manufactured by Corning Inc.) having a length of 100 mm, a width of 100 mm, and a width of 0.7 mm so that the film thickness after drying was 3.0 μm. The mixture was dried on a hot plate at ° C. for 1 minute. Next, ultraviolet exposure was performed under the conditions of an illuminance of 30 mW / cm ² and 40 mJ / cm ² using a high-pressure mercury lamp through a mask having a stripe pattern having a width of 100 μm. Then, it was immersed in an aqueous developer containing 0.12% of nonionic surfactant and 0.04% of potassium hydroxide at 23 ° C. for 40 seconds for development, and washed with pure water. The obtained pattern was observed on the surface of the pattern using an ECLIPSE LV100POL Model optical microscope manufactured by Nikon Corporation, and the degree of discoloration was evaluated. Make 3 or more practical.
5: There was no water stain.
4: Water stains were less than 10% of the total.
3: Water stains were 10% or more and less than 20% of the total.
2: Water stains were 20% or more and less than 30% of the total.
1: Water stain was 30% or more of the whole.

<Manufacturing of substrate for pattern formability evaluation>
The obtained photosensitive coloring composition is applied to a glass substrate (Eagle 2000 manufactured by Corning Inc.) having a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm by a spin coating method so that the film thickness after drying is 3.0 μm. It was processed and dried on a hot plate at 70 ° C. for 1 minute. Next, after cooling this substrate to room temperature, it was exposed to illuminances of 30 mW / cm ² and 40 mJ / cm ² using a high-pressure mercury lamp and a photomask having a 100 μm width (pitch 200 μm) and 10 μm width (pitch 20 μm) stripe pattern. .. Then, this substrate was spray-developed with an aqueous developer containing 0.12% by mass of a nonionic surfactant at 23 ° C. and 0.04% by mass of potassium hydroxide, washed with ion-exchanged water, and air-dried. , A substrate for evaluating pattern formability was obtained by heating at 230 ° C. for 30 minutes in a clean oven. The spray development was carried out for the coating film with each photosensitive coloring composition in the shortest time during which a pattern could be formed without any development residue.

[Evaluation of pattern formation (1): Adhesion]
Among the patterns for evaluating pattern formability prepared by the above method, a fine line pattern having a width of 6 to 25 μm was observed with an optical microscope, and the minimum line width of the remaining fine line pattern was confirmed. Make 3 or more practical.
Fine lines of 5:10 μm or less remain.
Thin lines of 4: 15 μm or less remain.
3: Fine lines of 20 μm or less remain.
Fine lines of 2: 25 μm or less remain.
1: No thin lines remain.

[Evaluation of pattern formability (2): Cross-sectional shape]
Using a scanning electron microscope (“S-3000H” manufactured by Hitachi High-Tech Co., Ltd.), the pattern shape of the substrate for pattern formability evaluation prepared by the above method was confirmed. For the evaluation, the cross-sectional shape was evaluated by capturing the SEM image of the cross section of the striped pattern having a width of 100 μm and measuring the taper angle between the base material and the end portion of the pattern cross section. Make 3 or more practical.
5: Taper angle 30 degrees or more and less than 50 degrees 4: Taper angle 50 degrees or more and less than 60 degrees 3: Taper angle less than 30 degrees or 60 degrees or more and less than 70 degrees 2: Taper angle 70 degrees or more and less than 90 degrees 1: Taper angle 90 degrees that's all

[Evaluation of pattern formation (3): Remaining film ratio]
At the time of preparing the above-mentioned substrate for pattern formability evaluation, spray development was performed, the film was washed with ion-exchanged water, and the film thickness of the coating film after air-drying was measured. This film thickness is defined as the post-development film thickness. Then, it was heated in a clean oven at 230 ° C. for 30 minutes, and the film thickness at the same place where the film thickness was measured after development was measured. This film thickness is defined as the post-baked film thickness. The residual film ratio was calculated from the two film thicknesses by the following formula. Make 3 or more practical. The film thickness was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).
Formula: Remaining film ratio (%) = film thickness after baking ÷ film thickness after development x 100
5: Residual film rate 85% or more 4: Residual film rate 80% or more and less than 85% 3: Residual film rate 75% or more and less than 80% 2: Residual film rate 70% or more and less than 75% 1: Residual film rate less than 70%

[Evaluation of surface wrinkles]
The surface of the pattern for evaluating the pattern formability was observed using an optical microscope (“BX-51” manufactured by Olympus Optical Co., Ltd., magnification: 200 times). Make 3 or more 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.

Claims (10)

A photosensitive coloring composition comprising a colorant (A), an alkali-soluble resin (B), a polymerizable compound (C), and a photopolymerization initiator (D).
A photosensitive coloring composition comprising the polymerizable compound (C) as an acid group-containing aromatic urethane (meth) acrylate (C1) and a lactone-modified (meth) acrylate (C2). The total content of the acid group-containing aromatic urethane (meth) acrylate (C1) and the lactone-modified (meth) acrylate (C2) is 20% by mass or more in 100% by mass of the polymerizable compound (C). The photosensitive coloring composition according to claim 1. Claim 1 or claim 1, wherein the polymerizable compound (C) further contains at least one selected from the group consisting of an aliphatic urethane (meth) acrylate (C3) and an alicyclic urethane (meth) acrylate (C4). 2. The photosensitive coloring composition according to 2. The ratio of the mass of the acid group-containing aromatic urethane (meth) acrylate (C1) to the total amount of the aliphatic urethane (meth) acrylate (C3) and the alicyclic urethane (meth) acrylate (C4) is The photosensitive coloring composition according to claim 3, which is 90:10 to 50:50. The photosensitive coloring composition according to any one of claims 1 to 4, wherein the photopolymerization initiator (D) contains an oxime compound (D1). The photosensitive coloring composition according to claim 5, wherein the oxime-based compound (D1) contains an oxime-based compound (D1-2) containing two oxime groups in one molecule. The photosensitive coloring composition according to any one of claims 1 to 6, further comprising a sensitizer (E). A color filter having a substrate and a filter segment formed by using the photosensitive coloring composition according to any one of claims 1 to 7. An image display device having the color filter according to claim 8. A solid-state image sensor having the color filter according to claim 8.