JP2023159490A - 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 high sensitivity and excellent storage stability and can form a color filter with less foreign matter generation and brightness reduction.SOLUTION: The photosensitive coloring composition contains a colorant (A), a dispersion resin (B), a polymerizable compound (C), and an oxime-based photopolymerization initiator (D). The dispersion resin (B) contains a dispersion resin (B1) having an acidic group. The total content of Li, Na, K, Mg, Ca, Fe, Al and Cr contained in the photosensitive coloring composition is 500 mass ppm or less, and the content of water is 2.0 mass% or less.SELECTED DRAWING: None

Description

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

Photosensitive coloring compositions used to manufacture color filters for use in image display devices, solid-state imaging devices, etc. are usually used after being stored for several weeks to several months after manufacture. In that case, there was a problem in that the viscosity and sensitivity of the photosensitive coloring composition changed depending on the storage period.

When the sensitivity of the photosensitive coloring composition changes, variations occur in developability, pattern shape, etc., and the quality of the color filter deteriorates.

In addition, important quality items required for color filters include contrast ratio and brightness, but there has been a problem that foreign matter is generated during heat treatment in the manufacturing process of color filters, resulting in a decrease in contrast and brightness. In addition, C.I., which is widely used as a green pigment. I. Pigment Green 7, C. I. Pigment Green 36, C. I. Pigment Green 58, C. I. Pigment Green 59, C. I. Pigment Green 62, C. I. Pigment Green 63, the zinc phthalocyanine pigment described in JP-A No. 2008-19383, JP-A 2007-320986, JP-A 2004-70342, etc.; A green filter segment using a phthalocyanine pigment and a yellow pigment, such as that disclosed in JP-A No. 2017-197685, has a problem in that its brightness decreases when it is incorporated into a liquid crystal display device and is illuminated by a backlight (Non-Patent Document 1).

In order to solve the above problems, for example, Patent Document 1 discloses an oxime having at least one type of group selected from a branched alkyl group and a cyclic alkyl group as a radiation-sensitive resin composition with excellent sensitivity stability over time. A radiation-sensitive resin composition containing an ester compound and having a water content of 0.1 to 2% by mass based on the mass of the radiation-sensitive resin composition is disclosed. Moreover, Patent Document 2 discloses reducing free copper in a pigment composition as a color filter pigment composition with excellent heat resistance that allows a liquid crystal display device with high contrast and high brightness to be obtained. Further, Patent Document 3 describes a coloring composition containing a halogenated zinc phthalocyanine pigment with excellent viscosity stability, in which the content of Group 2 element ions is 30 to 300 mass ppm based on the mass of the halogenated zinc phthalocyanine pigment. Certain colored compositions are disclosed.

International Publication No. 2017/099019 Japanese Patent Application Publication No. 2008-308605 Japanese Patent Application Publication No. 2015-166445

Journal of Photopolymer Science and Technology, Volume 7, Number 1 (1994) p. 151-158

However, none of the compositions described in Patent Documents 1 to 3 satisfy all of the storage stability (viscosity, sensitivity) and suppression of foreign matter generation. Furthermore, no consideration is given to the reduction in brightness when the display is incorporated into a liquid crystal display and there is a backlight.

An object of the present invention is to provide a photosensitive coloring composition that is highly sensitive, has excellent storage stability, and can form a color filter with less generation of foreign matter and less reduction in brightness.

The present invention is a photosensitive coloring composition comprising a colorant (A), a dispersion resin (B), a polymerizable compound (C), and an oxime photopolymerization initiator (D),
The dispersion resin (B) includes a dispersion resin (B1) having an acidic group,
The total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr contained in the photosensitive coloring composition is 500 mass ppm or less, and the water content is 2.0 mass% or less. This invention relates to a certain photosensitive coloring composition.

According to the above-mentioned present invention, it is possible to provide a photosensitive coloring composition that is highly sensitive, has excellent storage stability, and can form a color filter with less generation of foreign matter and less reduction in brightness. Further, the present invention can provide a color filter, a liquid crystal display device, and a solid-state image sensor.

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

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

<Photosensitive coloring composition>
One embodiment of the present invention relates to a photosensitive coloring composition. The photosensitive coloring composition of the present invention is a photosensitive coloring composition containing a colorant (A), a dispersion resin (B), a polymerizable compound (C), and an oxime photopolymerization initiator (D),
The dispersion resin (B) includes a dispersion resin (B1) having an acidic group,
The total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr contained in the photosensitive coloring composition is 500 mass ppm or less, and the water content is 2.0 mass% or less. It is a certain photosensitive coloring composition.

[Colorant (A)]
The photosensitive coloring composition of the present invention contains a colorant (A). The colorant (A) is not particularly limited, and may be either a pigment or a dye, and may be used in combination.

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

Red pigments that can be used in the present invention include, for example, 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: 3,81:4,83,88,90:1,101,101:1,104,108,108:1,109,112,113,114,122,123,144,146,147,149,151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281,282,283,284,285,286,287,291,295,296, pigments described in JP-A No. 2014-134712, pigments described in Japanese Patent No. 6368844, and the like. Among these, from the viewpoint of heat resistance, light resistance, and transmittance, C. I. Pigment Red 48:1,122,177,224,242,269,254,291,295,296, the pigment described in JP2014-134712A, the pigment described in Japanese Patent No. 6368844 are preferable, C. I. Pigment Red 177,254,291,295,296, the pigment described in Japanese Patent Application Publication No. 2014-134712, and the pigment described in Japanese Patent No. 6368844 are particularly preferred.

Orange pigments that can be used in the present invention include, for example, C.I. I. Pigment Orange 36, 38, 43, 64, 71, 73 and the like.

Yellow pigments that can be used in the present invention include, for example, 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, 192, 193, 194, 196, 198, 199, 213, 214, 231, 233, pigments described in JP 2012-226110 A, and the like. Among these, C. I. Pigment Yellow 138, 139, 150, 185, 231, 233 and the pigments described in JP 2012-226110 A are preferred.

Green pigments that can be used in the present invention include, for example, 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. Among these, C. I. Pigment Green 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 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. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, and 15:6 are 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, etc. Among these, C. I. Pigment Violet 19 and 23 are preferred.

Specifically, the black pigment that can be used in the present invention includes C.I. I. Pigment Black 1, 6, 7, 12, 20, 31 and the like. Alternatively, at least two or more pigments selected from red pigments, yellow pigments, blue pigments, green pigments, and violet pigments may be used as a black coloring agent.

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 white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, deep blue, chromium oxide green, cobalt green, amber, synthetic iron black, etc. can be mentioned.

(dye)
Examples of the dye include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. Also included are derivatives of these and lake pigments obtained by forming dyes into lakes.

It is preferable that the acidic dye has an acidic group such as sulfonic acid or carboxylic acid. Further, a salt-forming compound which is a salt of an acidic dye and a nitrogen-containing compound such as a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound is preferable. Also preferred are salt-forming compounds that are salts of resin components having these functional groups and acidic dyes. Further, by converting the salt-forming compound into a sulfonamide compound and modifying it into a sulfonic acid amide compound, a photosensitive composition with excellent resistance (light resistance, solvent resistance) can be easily obtained.
Further, a salt-forming compound of an acidic dye and a compound having an onium base is also preferable because it has excellent resistance (light resistance, solvent resistance). Note that the compound having an onium base is preferably a resin having a cationic group.

Although the basic dye can be used as it is, it is preferably a salt-forming compound that forms a salt with an organic acid, perchloric acid, or a metal salt thereof. Salt-forming compounds of basic dyes are preferable because they have excellent resistance (light resistance, solvent resistance) and affinity with pigments. In addition, the anion components that act as counter ions in the salt-forming compounds of basic dyes include organic sulfonic acids, organic sulfuric acids, fluorine group-containing phosphorus anion compounds, fluorine group-containing boron anion compounds, cyano group-containing nitrogen anion compounds, and carbonized halides. Preferred are salt forming compounds obtained by forming salts with an anionic compound having a conjugate base of an organic acid having a hydrogen group and an acidic dye. Note that the resistance of the salt-forming compound is further improved when it contains a polymerizable unsaturated group in the molecule.

The chemical structures of dyes include, for example, azo dyes, disazo dyes, azomethine dyes (indoaniline dyes, indophenol dyes, etc.), dipyrromethene dyes, quinone dyes (benzoquinone dyes, naphthoquinone dyes, anthraquinone dyes, etc.). dyes, anthrapyridone dyes, etc.), carbonium dyes (diphenylmethane dyes, triphenylmethane dyes, xanthene dyes, acridine dyes, etc.), quinone imine dyes (oxazine dyes, thiazine dyes, etc.), azine dyes , polymethine dyes (oxonol dyes, merocyanine dyes, arylidene dyes, styryl dyes, cyanine dyes, squarylium dyes, croconium dyes, etc.), quinophthalone dyes, phthalocyanine dyes, subphthalocyanine dyes, perinone dyes Examples include dye structures derived from dyes selected from dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and metal complex dyes thereof.

Among these, from the viewpoint of color characteristics such as hue, color separation, and color unevenness, azo dyes, xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, squarylium dyes, A dye structure derived from a dye selected from quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes is preferable, and dyes derived from xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are preferred. A dye structure derived from the selected dye is more preferred.

The colorant (A) can be used alone or in combination of two or more, and are mixed to obtain a desired color.

In the photosensitive coloring composition of the present invention, higher effects can be expected when a halogenated phthalocyanine pigment and a quinophthalone pigment are used together as the colorant (A).

The halogenated phthalocyanine pigment is C.I. I. Pigment Green 36, 58, 59, 62, and 63 are preferred, and C.I. I. Pigment Green 58 and 59 are more preferred.

The quinophthalone pigment is preferably a compound represented by the following general formula (2).
General formula (2)

In the general formula (2), R ₁ to R ₁₃ each independently represent a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkoxyl group that may have a substituent, and an alkyl group that may have a substituent. Indicates an aryl group that may be Adjacent groups R ₁ to R ₄ and/or R ₅ to R ₈ may be combined to form an aromatic ring which may have a substituent.

The substituents of R ₁ to R ₁₃ in general formula (2) will be explained.

Examples of halogen atoms include fluorine, chlorine, bromine, and iodine.

In addition, examples of alkyl groups that may have substituents include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, tert-butyl group, neopentyl group, n-hexyl group, n-octyl group. In addition to straight chain or branched alkyl groups such as stearyl group, 2-ethylhexyl group, trichloromethyl group, trifluoromethyl group, 2,2,2-trifluoroethyl group, 2,2-dibromoethyl group, 2,2,3,3-tetrafluoropropyl group, 2-ethoxyethyl group, 2-butoxyethyl group, 2-nitropropyl group, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4- Examples include alkyl groups having substituents such as methoxybenzyl group, 4-nitrobenzyl group, and 2,4-dichlorobenzyl group.

In addition, examples of the alkoxyl group which may have a substituent include a methoxy group, ethoxy group, propoxy group, isopropoxy group, n-butoxy group, isobutyloxy group, tert-butyloxy group, neopentyloxy group, 2,3 -In addition to linear or branched alkoxyl groups such as dimethyl-3-pentoxy, n-hexyloxy, n-octyloxy, stearyloxy, and 2-ethylhexyloxy, trichloromethoxy, trifluoromethoxy, , 2,2-trifluoroethoxy group, 2,2,3,3-tetrafluoropropyloxy group, 2,2-ditrifluoromethylpropoxy group, 2-ethoxyethoxy group, 2-butoxyethoxy group, 2-nitropropoxy group and an alkoxyl group having a substituent such as a benzyloxy group or a benzyloxy group.

Further, examples of the aryl group which may have a substituent include p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p-methylphenyl group, p-bromophenyl group, p-nitrophenyl group, p- Methoxyphenyl group, 2,4-dichlorophenyl group, pentafluorophenyl group, 2-aminophenyl group, 2-methyl-4-chlorophenyl group, 4-hydroxy-1-naphthyl group, 6-methyl-2-naphthyl group, 4 , 5,8-trichloro-2-naphthyl group, anthraquinonyl group, and 2-aminoanthraquinonyl group.

Adjacent groups R ₁ to R ₄ and/or R ₅ to R ₈ in general formula (2) are combined to form an aromatic ring which may have a substituent. The aromatic ring mentioned here includes a hydrocarbon aromatic ring and a heteroaromatic ring. Examples of the aromatic hydrocarbon ring include a benzene ring, a naphthalene ring, an anthracene ring, and a phenanthrene ring. Examples of heteroaromatic rings include pyridine ring, pyrazine ring, pyrrole ring, quinoline ring, quinoxaline ring, furan ring, benzofuran ring, thiophene ring, benzothiophene ring, oxazole ring, thiazole ring, imidazole ring, pyrazole ring, and indole ring. , carbazole ring, etc.

The quinophthalone pigment is C.I. I. Pigment Yellow 138 or quinophthalone pigments represented by the following general formulas (3) to (5) are preferred. Here, in R ₁₄ to R ₂₈ , R ₂₉ to R ₄₃ , R ₄₄ to R ₆₀ , a hydrogen atom, a halogen atom, an alkyl group that may have a substituent, an alkoxyl group that may have a substituent, The aryl group which may have a substituent has the same meaning as the group explained in general formula (2).

In general formulas (3) to (5), R ₁₄ to R ₂₈ , R ₂₉ to R ₄₃ , and R ₄₄ to R ₆₀ may each independently have a hydrogen atom, a halogen atom, a hydroxyl group, or a substituent. Indicates an alkyl group, an alkoxyl group that may have a substituent, and an aryl group that may have a substituent.

Furthermore, in the quinophthalone pigment used in the coloring composition of the present invention, R ₁₄ to R ₂₈ , R ₂₉ to R ₄₃ , and R ₄₄ to R ₆₀ of general formulas (3) to (5) are hydrogen atoms or halogen atoms. More preferred.

The quinophthalone pigment represented by the general formula (2) can be synthesized, for example, by the method described in JP-A-4-226163 and JP-A-2012-226110.

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

(Refining of pigment)
It is preferable to use the pigment in a finely divided form. The refinement method is not particularly limited, and, for example, any of wet milling, dry milling, and dissolution precipitation methods can be used. Among these, salt milling treatment using a kneader method, which is a type of wet milling, is preferred. The average primary particle diameter of the finely divided pigment determined by TEM (transmission electron microscope) is preferably 5 to 90 nm. Note that from the viewpoint of dispersibility and contrast ratio, the average primary particle diameter is more preferably 10 to 70 nm.

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

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

The water-soluble organic solvent functions to wet the pigment and the water-soluble inorganic salt, and is not particularly limited as long as it dissolves (mixes) in water and does not substantially dissolve the inorganic salt used. However, since the temperature rises during salt milling and the solvent is likely to evaporate, a high boiling point solvent with a boiling point of 120° C. or higher is preferred from the viewpoint of safety. For example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, Liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. are used. The amount of the water-soluble organic solvent used is preferably 5 to 1,000 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

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

[Dispersion resin (B)]
(Dispersed resin with acidic group (B1))
The photosensitive coloring composition of the present invention contains a dispersion resin (B1) having an acidic group as the dispersion resin (B). Thereby, it is possible to obtain a photosensitive coloring composition that has excellent storage stability and generates little foreign matter.

Examples of acidic groups include carboxyl groups, phosphoric acid groups, and sulfonic acid groups. Among these, from the viewpoint of storage stability and suppression of foreign substances, carboxyl groups and phosphoric acid groups are preferable, and carboxyl groups are more preferable.

The dispersion resin (B1) having an acidic group preferably contains a dispersion resin having a carboxyl group. For example, dispersion resins shown below (B1-1) or (B1-2) can be mentioned.

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

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

The tetracarboxylic dianhydride is not limited to the compounds exemplified above, and may have any structure as long as it has two carboxylic anhydride groups. These may be used alone or in combination. Tetracarboxylic dianhydride forms a dispersion resin having two carboxyl groups per unit of tetracarboxylic dianhydride through reaction with a hydroxyl group-containing compound, so from the viewpoint of pigment adsorption, the dispersion of the present invention is It is preferable as a constituent element of resin.

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

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

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

The molar ratio of the acid anhydride group in one or more acid anhydrides selected from the tetracarboxylic dianhydride and tricarboxylic acid anhydride to the hydroxyl group in the hydroxyl group-containing compound is acid anhydride group/hydroxyl group=0. 5 to 1.5 is preferred. When the reaction is carried out at an appropriate ratio, it is easy to obtain a dispersed resin with good dispersibility.

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

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

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

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

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

(i-2) [Oxetane group-containing monomer]
Examples of the monomer having an oxetane group as a thermally crosslinkable group include (vinyloxyalkyl)alkyloxetane, (meth)acryloyloxyalkyloxetane, and [(meth)acryloyloxyalkyl]alkyloxetane. Among them, (3-ethyloxetan-3-yl)methyl methacrylate and the like are preferred. Examples of commercially available products include ETERNACOLL OXMA ((3-ethyloxetan-3-yl)methyl methacrylate) (manufactured by Ube Industries, Ltd.).

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

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

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

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

(iii) [Other monomers]
For the vinyl polymer portion of the acidic group-containing dispersion resin (B1-1-1), other monomers than the thermally crosslinkable monomer and the carboxyl group-containing monomer can be used.
Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, 2 - Alkyl (meth)acrylates such as ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, trimethylcyclohexyl (meth)acrylate, isobornyl (meth)acrylate;
Aromatic (meth)acrylates such as phenyl (meth)acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate;
Heterocyclic (meth)acrylates such as tetrahydrofurfuryl (meth)acrylate;
Alkoxypolyalkylene glycol (meth)acrylates such as methoxypolypropylene glycol (meth)acrylate and ethoxypolyethylene glycol (meth)acrylate;
N-substituted (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone(meth)acrylamide, acryloylmorpholine, etc. Acrylamides;
Amino group-containing (meth)acrylates such as N,N-dimethylaminoethyl (meth)acrylate and N,N-diethylaminoethyl (meth)acrylate;
and nitriles such as (meth)acrylonitrile.

Also included are styrenes such as styrene and α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether, and fatty acid vinyls such as vinyl acetate and vinyl propionate. .

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

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

[Dispersion resin with acidic group (B1-2)]
The dispersion resin (B1-2) having an acidic group is a dispersion resin represented by the following general formula (6), and specifically, it is a dispersion resin described in JP-A No. 2007-140487.

General formula (6)
(HOOC-) _m -R ² -(-COO-[-R ⁴ -COO-] _n -R ⁵ ) _t
(In general formula (6), R ² is a tetravalent tetracarboxylic acid compound residue, R ⁵ is a monoalcohol residue, R ⁴ is a lactone residue, m is 2 or 3, and n is an integer from 1 to 50. , t represents (4-m).)

The acid value of the dispersion resin (B1) having an acidic group is preferably 20 to 250 mgKOH/g, more preferably 30 to 200 mgKOH/g, from the viewpoint of storage stability and foreign matter suppression.

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

The content of the dispersion resin (B1) having an acidic group is preferably 3 to 200 parts by mass, and 5 to 100 parts by mass, based on 100 parts by mass of the colorant (A), from the viewpoint of storage stability and foreign matter suppression. More preferred.

[Dispersion resin with basic group (B2)]
From the viewpoint of storage stability, the photosensitive coloring composition of the present invention preferably further contains a dispersion resin (B2) having a basic group.

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

The dispersion resin (B2) having a basic group has at least one unit selected from the group represented by the following general formula (7), general formula (8), and general formula (9) as a basic group. It is preferable.

General formula (7)

(In general formula (7), R ₁ to R ₃ each independently represent a hydrogen atom or a chain or cyclic hydrocarbon group that may have a substituent, and each of R ₁ to R ₃ Two or more of them may combine with each other to form a cyclic structure. R ₄ represents a hydrogen atom or a methyl group, X represents a divalent linking group, and Y ⁻ represents a counter anion.)

（ 一般式（８）中、Ｒ_５、およびＲ_６は、相互に独立に、水素原子、又は置換基を有していてもよい鎖状若しくは環状の炭化水素基を示し、Ｒ_５、およびＲ_６が互いに結合して環状構造を形成してもよい。Ｒ_４は水素原子又はメチル基を示し、Ｘは２価の連結基を示す。） General formula (8)

(In general formula (8), R ₅ and R ₆ independently represent a hydrogen atom or a chain or cyclic hydrocarbon group which may have a substituent, and R ₅ and R ₆ may combine with each other to form a cyclic structure. R ₄ represents a hydrogen atom or a methyl group, and X represents a divalent linking group.)

（ 一般式（９）中、Ｒ_７は水素原子、炭素数１～１８のアルキル基、炭素数６～２０のアリール基、炭素数７～１２のアラルキル基、アシル基、オキシラジカル基、またはＯＲ_１２を表し、Ｒ_１２は、水素原子、炭素数１～１８のアルキル基、炭素数６～２０のアリール基、炭素数７～１２のアラルキル基、またはアシル基を表し、Ｒ_８、Ｒ_９、Ｒ_１０、Ｒ_１１はそれぞれ独立に、メチル基、エチル基、またはフェニル基を示す。Ｒ_４は水素原子又はメチル基を示し、Ｘは２価の連結基を示す。） General formula (9)

(In the general formula (9), R ₇ is a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, an acyl group, an oxyradical group, or an OR ₁₂ , R ₁₂ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, an aryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 12 carbon atoms, or an acyl group, R ₈ , R ₉ , R ₁₀ and R ₁₁ each independently represent a methyl group, an ethyl group, or a phenyl group. _{R 4} represents a hydrogen atom or a methyl group, and X represents a divalent linking group.)

R ₁ to R ₃ in general formula (7) are, for example, an alkyl group having 1 to 4 carbon atoms which may have a substituent, or an aralkyl group having 7 to 16 carbon atoms which may have a substituent. are more preferred, and methyl, ethyl, propyl, butyl, and benzyl groups are particularly preferred.

R ₅ and R ₆ in general formula (8) are, for example, more preferably an alkyl group having 1 to 4 carbon atoms which may have a substituent, and particularly preferably a methyl group, an ethyl group, a propyl group, or a butyl group. .

In R ₇ of the general formula (9), examples of the alkyl group having 1 to 18 carbon atoms include linear, branched, and cyclic alkyl groups, and specifically, methyl group, ethyl group, normal propyl group, etc. group, isopropyl group, n-butyl group, t-butyl group, n-hexyl group, cyclohexyl group, n-octyl group, hexadecyl group and the like.
Examples of the aryl group having 6 to 20 carbon atoms include phenyl group, 1-naphthyl group, and 2-naphthyl group.
Examples of the aralkyl group having 7 to 12 carbon atoms include a group in which an alkyl group having 1 to 8 carbon atoms is bonded to an aryl group having 6 to 10 carbon atoms, and specifically, a benzyl group, a phenethyl group, Examples include α-methylbenzyl group and 2-phenylpropan-2-yl group.
Further, examples of the acyl group include an alkanoyl group having 2 to 8 carbon atoms and an aroyl group, and specific examples include an acetyl group and a benzoyl group.
Among these, a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, and an oxy radical group are particularly preferred, a hydrogen atom and a methyl group are more preferred, and a methyl group is most preferred.

In general formulas (7) to (9), the divalent linking group X is, for example, a methylene group, an alkylene group having 2 to 10 carbon atoms, an arylene group, -CONH-R ₁₃ -, -COO-R ₁₄ -( However, R ₁₃ and R ₁₄ are a single bond, a methylene group, an alkylene group having 2 to 10 carbon atoms, or an ether group (alkyloxyalkyl group) having 2 to 10 carbon atoms, and preferably - COO-R _{1 4} -. Further, in general formula (7), examples of the counter anion Y ⁻ include Cl ⁻ , Br ⁻ , I ⁻ , ClO ₄ ⁻ , BF ₄ ⁻ , CH ₃ COO ⁻ , PF ₆ ⁻ and the like.

Examples of the quaternary ammonium base-containing monomer serving as the precursor/partial structure of general formula (7) include (meth)acryloyloxyethyltrimethylammonium chloride, (meth)acryloyloxyethyltriethylammonium chloride, and (meth)acryloyl Alkyl (meth)acrylate quaternary ammonium salts such as oxyethyldimethylbenzylammonium chloride, (meth)acryloyloxyethylmethylmorpholinoammonium chloride, (meth)acryloylaminopropyltrimethylammonium chloride, (meth)acryloylaminoethyltriethylammonium chloride , (meth)acryloylamide quaternary ammonium salts such as (meth)acryloylaminoethyldimethylbenzylammonium chloride, dimethyldiallylammonium methyl sulfate, trimethylvinylphenylammonium chloride, and the like.

The tertiary amine group-containing monomer that becomes the precursor/partial structure of general formula (8) is, for example, N,N-dimethylaminoethyl (meth)acrylate, N,N-diethylaminoethyl (meth)acrylate, N , N-dimethylaminopropyl (meth)acrylate, N,N-diethylaminopropyl (meth)acrylate and other (meth)acrylates having a tertiary amino group;
Tertiary compounds such as N,N-dimethylaminoethyl (meth)acrylamide, N,N-diethylaminoethyl (meth)acrylamide, N,N-dimethylaminopropyl (meth)acrylamide, and N,N-diethylaminopropyl (meth)acrylamide Examples include (meth)acrylamides having an amino group.

Examples of the monomer serving as the precursor/partial structure of general formula (9) include compounds represented by the following general formulas (9-1) to (9-11).

In general formulas (9-1) to (9-11), R ₄ represents hydrogen or a methyl group.

Among these, 2,2,6,6-tetramethylpiperidyl methacrylate (a compound in which R ₄ is a methyl group in general formula (9-1)), 1,2,2,6,6-pentamethylpiperidyl methacrylate (Compounds in which R ₄ is a methyl group in general formula (9-2)) are preferred, and 1,2,2,6,6-pentamethylpiperidyl methacrylate is particularly preferred.

The units represented by general formulas (7) to (9) may be contained alone or in combination of two or more, and may be contained in any form of random copolymerization, block copolymerization, or graft copolymerization. , is more preferably contained in the form of a block copolymer.

The units represented by general formulas (7) to (9) are not particularly limited as long as they have a structure obtained by copolymerizing copolymerizable monomers, and can be appropriately selected depending on the purpose. Copolymerizable monomers are shown below.

For example, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth), tert-butyl (meth)acrylate, isoamyl (meth)acrylate , octyl (meth)acrylate, isooctyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cetyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, lauryl (meth)acrylate, tridecyl (meth)acrylate , linear or branched alkyl (meth)acrylates such as isomyristyl (meth)acrylate, stearyl (meth)acrylate, and isostearyl (meth)acrylate;
Cyclic alkyl (meth)acrylates such as cyclohexyl (meth)acrylate, tert-butylcyclohexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, dicyclopentenyl (meth)acrylate, and isobornyl (meth)acrylate;
(meth)acrylates having a heterocycle such as tetrahydrofurfuryl (meth)acrylate and 3-methyl-3-oxetanyl (meth)acrylate;
(Meth)acrylates having an aromatic ring such as benzyl (meth)acrylate and phenoxyethyl (meth)acrylate; 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, 2-methoxypropyl (meth)acrylate , diethylene glycol monomethyl ether (meth)acrylate, diethylene glycol monoethyl ether (meth)acrylate, diethylene glycol mono-2-ethylhexyl ether (meth)acrylate, dipropylene glycol monomethyl ether (meth)acrylate, triethylene glycol monomethyl ether (meth)acrylate, Triethylene glycol monoethyl ether (meth)acrylate, tripropylene glycol monomethyl ether (meth)acrylate, tetraethylene glycol monomethyl ether (
meth)acrylate, polyethylene glycol monomethyl ether (meth)acrylate, polypropylene glycol monomethyl ether (meth)acrylate, polyethylene glycol monolauryl ether (meth)acrylate, polyethylene glycol monostearyl ether (meth)acrylate, and octoxypolyethylene glycol-polypropylene glycol (Poly)alkylene glycol monoalkyl ether (meth)acrylates such as (meth)acrylate;
Phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, paracumylphenoxyethyl (meth)acrylate, paraacrylate Milphenoxyethylene glycol (meth)acrylate, paracumylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, and nonylphenoxypoly(ethylene glycol-propylene glycol) (meth)acrylate. ) (Poly)alkylene glycol (meth)acrylates having an aromatic ring such as acrylate;
Alkyloxy such as 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxysilane, and 3-acryloxypropyltrimethoxysilane (Meth)acrylates having a silyl group;
Fluoroalkyl (meth)acrylates such as trifluoroethyl (meth)acrylate, octafluoropentyl (meth)acrylate, perfluorooctylethyl (meth)acrylate, and tetrafluoropropyl (meth)acrylate; (meth)acryloxy-modified polydimethyl Siloxanes (silicone macromers);
N-substituted (meth)acrylamides such as (meth)acrylamide, dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, and acryloylmorpholine; Additionally, nitriles such as (meth)acrylonitrile and the like can be mentioned.
Also, styrenes such as styrene and α-methylstyrene; vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, and isobutyl vinyl ether; and fatty acids such as vinyl acetate and vinyl propionate. Examples include vinyls.

Furthermore, a carboxyl group-containing monomer can also be used in combination. Examples of carboxyl group-containing monomers include (meth)acrylic acid, (meth)acrylic acid dimer, itaconic acid, maleic acid, fumaric acid, crotonic acid, 2-(meth)acryloyloxyethyl phthalate, and 2-(meth)acrylic acid dimer. ) Acryloyloxypropyl phthalate, 2-(meth)acryloyloxyethyl hexahydrophthalate, 2-(meth)acryloyloxypropyl hexahydrophthalate, β-carboxyethyl (meth)acrylate, and ω-carboxypolycaprolactone (meth) ) acrylate, etc.

Furthermore, amino group-containing monomers other than the units represented by general formulas (7) to (9) may be used in combination within a range that does not impair the effects of the present invention.

Also preferably used is a resin in which some of the basic groups of the dispersion resin (B2) having a basic group are combined with a compound represented by the following general formula (10) or (11) to form a salt. be able to.

（一般式（１０）中、Ｒ^１、およびＲ^２はそれぞれ独立に、水素原子、水酸基、炭素数１～２０の直鎖、分岐鎖または環状のアルキル基、ビニル基、置換基を有してもよいフェニル基またはベンジル基、または－Ｏ－Ｒ^４を表し、Ｒ^４は、炭素数１～２０の直鎖、分岐鎖または環状のアルキル基、ビニル基、置換基を有してもよいフェニル基またはベンジル基、または炭素数１～４のアルキレン基を介した（メタ）アクリロイル基を表す。但し、Ｒ^１、およびＲ^２の少なくとも一つは炭素原子を含む基である。） General formula (10)

(In general formula (10), R ¹ and R ² each independently have a hydrogen atom, a hydroxyl group, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or a substituent. R 4 represents a phenyl group or a benzyl group, which may optionally be a phenyl group or a benzyl group, or -O-R ⁴ , and R ⁴ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, or a phenyl group which may have a substituent. or a benzyl group, or a (meth)acryloyl group via an alkylene group having 1 to 4 carbon atoms.However, at least one of R ¹ and R ² is a group containing a carbon atom.)

（一般式（１１）中、Ｒ^３は、炭素数１～２０の直鎖、分岐鎖または環状のアルキル基、ビニル基、置換基を有してもよいフェニル基またはベンジル基、または－Ｏ－Ｒ^４を表し、Ｒ^４は、炭素数１～２０の直鎖、分岐鎖または環状のアルキル基、ビニル基、置換基を有してもよいフェニル基またはベンジル基、または炭素数１～４のアルキレン基を介した（メタ）アクリロイル基を表す。） General formula (11)

(In general formula (11), R ³ is a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or -O- R ⁴ represents a straight chain, branched or cyclic alkyl group ^having 1 to 20 carbon atoms, a vinyl group, a phenyl group or benzyl group which may have a substituent, or a C 1 to 4 straight chain, branched or cyclic alkyl group, or (Represents a (meth)acryloyl group via an alkylene group.)

Examples of the compound represented by the general formula (10) include monobutyl phosphoric acid, dibutyl phosphoric acid, methyl phosphoric acid, dibenzyl phosphoric acid, diphenyl phosphoric acid, phenylphosphinic acid, phenylphosphonic acid, dimethacryloyloxyethyl acid phosphate, and the like.

Examples of the compound represented by the general formula (11) include benzenesulfonic acid, vinylsulfonic acid, methanesulfonic acid, p-toluenesulfonic acid, monomethyl sulfate, monoethyl sulfate, mono-n-propyl sulfate, and the like. Note that a hydrate such as p-toluenesulfonic acid monohydrate may also be used.

From the viewpoint of storage stability, the amine value of the dispersion resin (B2) having a basic group is preferably 20 to 250 mgKOH/g, more preferably 30 to 150 mgKOH/g.

The dispersion resin (B2) having a basic group can be used alone or in combination of two or more types.

From the viewpoint of storage stability, the content of the dispersion resin (B2) having a basic group is preferably 3 to 200 parts by mass, more preferably 5 to 100 parts by mass, based on 100 parts by mass of the colorant (A). .

The mass ratio of the dispersion resin (B1) having an acidic group and the dispersion resin (B2) having a basic group is:
From the viewpoint of storage stability and foreign matter suppression, the ratio is preferably 100:0 to 30:70, more preferably 70:30 to 30:70.

The content of the dispersion resin (B) is preferably 3 to 200 parts by weight, more preferably 5 to 100 parts by weight, based on 100 parts by weight of the colorant (A), from the viewpoint of storage stability and foreign matter suppression.

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

Examples of the polymerizable compound (C) include monomers and oligomers. Examples of the polymerizable unsaturated group include a vinyl group, a (meth)allyl group, a (meth)acryloyl group, and a (meth)acryloyloxy group. Examples of the polymerizable compound (C) include lactone-modified polymerizable compounds, acidic group-containing polymerizable compounds, urethane bond-containing polymerizable compounds, and other polymerizable compounds.

(Lactone-modified polymerizable compound)
The photosensitive coloring composition of the present invention preferably contains a lactone-modified polymerizable compound from the viewpoint of coating film resistance.

A lactone-modified polymerizable compound is a compound that has a lactone-modified structure in its molecule. Lactone-modified polymerizable compounds include polyhydric alcohols such as trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaethythritol, tripentaerythritol, glycerin, diglycerol, and trimerolmelamine; It is obtained by esterifying meth)acrylic acid and ε-caprolactone or other lactone compounds. The lactone-modified polymerizable compound is preferably a compound represented by the following general formula (12).

General formula (12)

In general formula (12), all 6 R's are groups represented by the following general formula (13), or 1 to 5 of the 6 R's are groups represented by the following general formula (13). , the remainder is a group represented by the following general formula (14).

General formula (13)

In the general formula (13), R ¹ represents a hydrogen atom or a methyl group, m is an integer of 1 or 2, and * is a bond bonding to the oxygen atom of the general formula (12).

General formula (14)

In the general formula (14), R ¹ represents a hydrogen atom or a methyl group, and * is a bond bonded to the oxygen atom of the general formula (12).

The lactone-modified polymerizable compound is, for example, commercially available as KAYARAD DPCA series manufactured by Nippon Kayaku Co., Ltd., and DPCA-20 (in the above general formulas (12) to (14), m=1, general formula ), the number of groups represented by = 2, R ¹ is all hydrogen atoms), DPCA-30 (in the above general formulas (12) to (14), m = 1, a compound represented by general formula (13)) number of groups = 3, R ¹ is all hydrogen atoms), DPCA-60 (in the above general formulas (12) to (14), m = 1, the number of groups represented by general formula (13) = 6, compound in which R ¹ is all hydrogen atoms), DPCA-120 (in the above general formulas (12) to (14), m = 2, number of groups represented by general formula (13) = 6, R Compounds in which all ¹ are hydrogen atoms), etc.

From the viewpoint of coating film resistance, the lactone-modified polymerizable compound has m=1 in the above general formulas (12) to (14), the number of groups represented by general formula (13)=2 to 6, and R Compounds in which all ¹ are hydrogen atoms are preferred, and in the above general formulas (12) to (14), m = 1, the number of groups represented by general formula (13) = 2 or 3, and all R ¹ are hydrogen atoms. More preferred are compounds where

From the viewpoint of coating film resistance, the content of the lactone-modified polymerizable compound is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and more preferably 20 to 60% by mass based on 100% by mass of the polymerizable compound (C). More preferably, it is expressed in mass %.

(Polymerizable compound with acidic group)
The photosensitive coloring composition of the present invention preferably contains a polymerizable compound having an acidic group from the viewpoint of alkali developability and pattern formation. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups. Among these, carboxyl groups are preferred.

Polymerizable compounds having acidic groups include, for example, esterification products of free hydroxyl group-containing poly(meth)acrylates of polyhydric alcohols and (meth)acrylic acid, and dicarboxylic acids; polyhydric carboxylic acids and monohydroxyalkyl ( Examples include esterification products with meth)acrylates.
Examples of the polyhydric alcohol include ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerin, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, and the like.
Examples of dicarboxylic acids include malonic acid, succinic acid, maleic acid, glutaric acid, phthalic acid, itaconic acid, and the like.
Examples of polyhydric carboxylic acids include trimellitic acid and pyromellitic acid.
Examples of monohydroxyalkyl (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, and pentaerythritol. Examples include triacrylate, 2-hydroxy-3-acryloyloxypropyl methacrylate, and the like.

Commercially available polymerizable compounds having acidic groups include Viscoat #2500P manufactured by Osaka Organic Co., Ltd., Aronix M-5300, M-5400, M-5700, M-510, M-520, M-521 manufactured by Toagosei Co., Ltd. can be mentioned.

The content of the polymerizable compound having an acidic group is preferably 5 to 80% by mass, and preferably 10 to 70% by mass based on 100% by mass of the polymerizable compound (C) from the viewpoint of alkali developability and pattern forming property. is more preferable, and even more preferably 20 to 60% by mass.

(Polymerizable compound with urethane bond)
The photosensitive coloring composition of the present invention preferably contains a polymerizable compound having a urethane bond as the polymerizable compound (C) from the viewpoint of pattern forming properties.

Polymerizable compounds having a urethane bond include, for example, urethane (meth)acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, or a compound obtained by reacting a polyhydric alcohol with a polyfunctional isocyanate and further having a hydroxyl group. Examples include urethane (meth)acrylate obtained by reacting (meth)acrylate.

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

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

The polymerizable compound having a urethane bond may further have an acidic group from the viewpoint of developability. Examples of acidic groups include sulfonic acid groups, carboxyl groups, and phosphoric acid groups. Among these, a carboxyl group is preferred.

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

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

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

From the viewpoint of pattern formation, the content of the polymerizable compound having a urethane bond is preferably 5 to 80% by mass, more preferably 10 to 70% by mass, and more preferably 20 to 60% by mass based on 100% by mass of the polymerizable compound (C). Mass % is more preferred.

(Other polymerizable compounds)
Other polymerizable compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, and β-carboxyethyl (meth)acrylate. ) acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetra Ethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, trimethylolpropane PO modified tri(meth)acrylate, trimethylolpropane EO modified tri(meth)acrylate, isocyanuric acid EO modified di(meth)acrylate, isocyanuric acid EO modified tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, 1,6-hexanediol diglycidyl ether di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl(meth)acrylate, methyl - Various acrylic esters and methacrylic esters such as (meth)acrylic ester of melamine, epoxy (meth)acrylate, urethane acrylate, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, Examples include (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile.

Other commercially available polymerizable compounds include, for example, KAYARAD R-128H, R526, PEG400DA, MAND, NPGDA, R-167, HX-220, R-551, R712, R-604, R- manufactured by Nippon Kayaku Co., Ltd. 684, GPO-303, TMPTA, DPHA, DPEA-12, DPHA-2C, D-310, D-330, and Aronix M-303, M-305, M-306, M-309, M manufactured by Toagosei Co., Ltd. -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, Viscoat #310HP, #335HP, #700, #295, #330, #360, #GPT, #400 manufactured by Osaka Organic Co., Ltd. , #405, OGSOL EA-0200, EA-0300, GA-5060P, GA-2800 manufactured by Osaka Gas Chemical Co., Ltd., Miwon Specialty Chemical Co. , Ltd. Miramer HR6060, 6100, 6200, Shin-Nakamura Chemical Industry Co., Ltd. NK ester ABE-300, A-DOG, A-DCP, A-BPE-4, A-9300, Daicel Allnex Corporation EBECRYL40. , 130, 140, 145, etc.

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

The polymerizable compound (C) is one selected from the group consisting of lactone-modified polymerizable compounds, acidic group-containing polymerizable compounds, and urethane bond-containing polymerizable compounds from the viewpoint of coating film resistance and pattern formation. It is preferable to include one or more types.

The content of the polymerizable compound (C) is 1 to 6% in 100% by mass of nonvolatile content of the photosensitive coloring composition.
0% by weight is preferable, and 2 to 50% by weight is more preferable.

[Oxime-based photopolymerization initiator (D)]
The photosensitive coloring composition of the present invention contains an oxime photopolymerization initiator (D). Thereby, a highly sensitive photosensitive coloring composition can be obtained.

Commercially available oxime photopolymerization initiators (D) include IRGACURE OXE-01, 02, 03, 04 manufactured by BASF Japan, and ADEKA Arkles N-1919, NCI-730, 831, 930 manufactured by ADEKA. , TRONLY TR-PBG-301, 304, 305, 309, 314, 345, 346, 358, 365, 380, 610, 3054, 3057 manufactured by Changzhou Strong New Materials, OMNIRAD1312, 1314, 1316 manufactured by IGM Resins, Examples include SPI-02, 03, 04, 05, 06, 07 manufactured by Samyang Corporation, and DFI-020, 306 and EOX-01 manufactured by Daito Chemix. In addition, compounds described in JP-A No. 2001-233842, compounds described in JP-A No. 2000-080068, compounds described in JP-A No. 2006-342166, compounds described in JP-A No. 2000-066385, Compounds described in JP-A No. 2000-080068, compounds described in Japanese Patent Application Publication No. 2004-5347797, compounds described in JP-A No. 2006-342166, compounds described in JP-A No. 2017-019766, patent no. Compounds described in WO 2015/152153, compounds described in WO 2017/051680, compounds described in JP 2017-198865, WO 2017/164127 Compounds described in JP-A No. 2014-137466, compounds described in JP-A No. 2010-262028, compounds described in Japanese Patent Application Publication No. 2014-500852, compounds described in JP-A No. 2013-164471 Compounds described in JP 2013-114249, compounds described in JP 2014-137466, compounds described in Patent No. 4223071, compounds described in International Publication No. 2015/036910, Compounds described in Japanese Patent Application Publication No. 2012-526185, Compounds described in Japanese Patent Application Publication No. 2012-519191, Compounds described in Japanese Patent Application Publication No. 2017-512886, Compounds described in Japanese Patent Application Publication No. 2015-523318, Compounds described in Japanese Patent Application Publication No. 2015-523318, Examples include compounds described in JP-A No. 2016-519675, compounds described in JP-A No. 2017-061498, and compounds described in Japanese Patent Publication No. 2017-523465.

(Compound (D1) represented by general formula (1))
The oxime-based photopolymerization initiator (D) preferably contains a compound (D1) represented by the following general formula (1) from the viewpoint of sensitivity and storage stability.
General formula (1)


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

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

In the general formula (1), R ₂ is an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an arylalkyl group having 2 to 20 carbon atoms. Represents a heterocyclic group.
The alkyl group having 3 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof; for example, propyl group, isopropyl group, butyl group, isobutyl group, t -Butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group , cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, and the like.
Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, and anthryl group.
Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, and phenylethyl group.
Examples of the heterocyclic group having 2 to 20 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, a morpholinyl group, and the like.
Among the above, from the viewpoint of storage stability, alkyl groups having 3 to 20 carbon atoms are preferred, alkyl groups having 3 to 8 carbon atoms are more preferred, and pentyl groups are particularly preferred.

In the general formula (1), R ₃ is an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or an arylalkyl group having 2 to 20 carbon atoms. Represents a heterocyclic group.
The alkyl group having 3 to 20 carbon atoms may be linear, branched, cyclic, or a combination thereof; for example, propyl group, isopropyl group, butyl group, isobutyl group, t -Butyl group, pentyl group, isopentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, hexadecyl group, cyclopentyl group , cyclopentylmethyl group, cyclohexyl group, cyclohexylmethyl group, cyclohexylmethyl group, and the like.
Examples of the aryl group having 6 to 30 carbon atoms include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, and anthryl group.
Examples of the arylalkyl group having 7 to 30 carbon atoms include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, and phenylethyl group.
Examples of the heterocyclic group having 2 to 20 carbon atoms include a pyridyl group, a pyrimidyl group, a furyl group, a tetrahydrofuryl group, a dioxolanyl group, an imidazolidyl group, an oxazolidyl group, a piperidyl group, a morpholinyl group, and the like.
Among the above, from the viewpoint of storage stability, a branched alkyl group having 3 to 15 carbon atoms is preferable, a branched alkyl group having 5 to 12 carbon atoms is more preferable, and 3-methylbutyl group, 2-ethylhexyl group, etc. Particularly preferred are groups.

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

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

The method for producing the compound (D1) represented by general formula (1) is not particularly limited, and known methods can be used. For example, methods described in International Publication No. 2008/078678, International Publication No. 2014/050738, Japanese Patent Application Publication No. 2016-519675, etc. can be used.

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

Among the compounds of chemical formulas (15) to (20), the compound of chemical formula (20) is preferred because it has high stability against metal ions and water and is difficult to decompose over time.

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

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

(Other photopolymerization initiators (F))
The photosensitive coloring composition of the present invention may contain a photopolymerization initiator (F) other than the oxime photopolymerization initiator (D) (hereinafter also referred to as other photopolymerization initiator (F)) within a range that does not impair the effects of the present invention. ).

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

Other photoinitiators (F) include 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl Propan-1-one, 1-hydroxycyclohexylphenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4- (4-morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl ]-Acetophenone photopolymerization initiator such as 1-butanone;
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl -A benzophenone photopolymerization initiator such as 4'-methyldiphenyl sulfide or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone;
2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s -triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-triazine methyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4 , 6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, or 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine. photopolymerizable initiator;
Initiation of photopolymerization of acylphosphine oxides such as 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or diphenyl-2,4,6-trimethylbenzoylphosphine oxide agent;
2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl))4,4',5,5'- Tetraphenylbiimidazole, 2,2'-bis(o,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4' , 5,5'-tetra(m-methoxyphenyl)biididazole, 2,2'-bis(o,o'-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'- Bis(o-nitrophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-methylphenyl)-4,4',5,5'-tetraphenylbiimidazole , 2,2'-bis(o-trifluorophenyl)-4,4',5,5'-tetraphenylbiimidazole and other imidazole-based photopolymerization initiators.
Among these, acetophenone-based photopolymerization initiators and acylphosphine oxide-based polymerization initiators are preferred from the viewpoint of developability and pattern-forming properties.

Commercially available acetophenone photopolymerization initiators include Omnirad 907, 369, and 379EG manufactured by IGM Resins.
Commercially available acylphosphine oxide polymerization initiators include Omnirad 819 and TPO manufactured by IGM Resins.

Other photopolymerization initiators (F) can be used alone or in combination of two or more.

[Copper salt of quinophthalone compound having sulfo group (E)]
The photosensitive coloring composition of the present invention preferably contains a copper salt (E) of a quinophthalone compound having a sulfo group from the viewpoint of suppressing a decrease in brightness.

A quinophthalone compound is a compound having a structure represented by the following chemical formula (21). Specifically, C. I. Commercially available dyes such as Acid Yellow 3 and 5, and C.I. I. Pigment Yellow 138, C. I. Solvent Yellow 33, 114, 157, C.I. I. Commercially available pigments and dyes such as Disperse Yellow 54, 64, and 67 may be mentioned.

Chemical formula (21)

A quinophthalone compound having a sulfo group is a compound obtained by sulfonating a compound having a structure represented by the chemical formula (21) using a known method, and specifically includes the following, but the present invention It is not limited to these.

The copper salt (E) of a quinophthalone compound having a sulfo group can be obtained by counter-exchanging --SO ₃ H of the above-mentioned exemplary compound to a copper salt by a known method.

The copper salt (E) of a quinophthalone compound having a sulfo group can be used alone or in combination of two or more kinds.

The content of the copper salt (E) of the quinophthalone compound having a sulfo group is preferably 1 to 40 parts by mass, and 5 to 30 parts by mass, based on 100 parts by mass of the colorant (A), from the viewpoint of suppressing a decrease in brightness. is more preferable.

Moreover, the photosensitive coloring composition of the present invention can contain a metal salt other than copper, such as the copper salt (E) of a quinophthalone compound having a sulfo group. Examples of metals include aluminum, zinc, nickel, iron, and the like.

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

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

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

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

(Photosensitive binder resin)
The photosensitive binder resin is a binder resin having a polymerizable unsaturated group. The photosensitive binder resin is preferably a resin synthesized by the following method (i) or (ii), for example. By curing with active energy rays, the resin undergoes three-dimensional crosslinking, improving crosslinking density and improving chemical resistance.

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

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

Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, n-propyl (meth)acrylate, isopropyl (meth)acrylate, n-butyl (meth)acrylate, isobutyl (meth)acrylate, t- Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate Acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, ethoxypolyethylene glycol (meth)acrylate, ethylene oxide (EO) modified cresol acrylate, n-nonyl Phenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, EO-modified (meth)acrylate of phenol, EO- or propylene oxide (PO)-modified (meth)acrylate of paracumylphenol, EO-modified (meth)acrylate of nonylphenol, nonylphenol (meth)acrylates such as PO-modified (meth)acrylate;
(Meth)acrylamides such as (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, diacetone (meth)acrylamide, or acryloylmorpholine. ;
Styrene or styrenes such as α-methylstyrene;
Vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether;
Fatty acid vinyls such as vinyl acetate or vinyl propionate;
Cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylene dimaleimide, N,N'-1,4-phenylene di Maleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl N-substituted maleimides such as -6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine;
2-(meth)acryloyloxyethyl acid phosphate, a phosphoric acid ester group-containing monomer such as a compound in which a phosphoric acid esterification agent such as phosphorus pentoxide or polyphosphoric acid is reacted with the hydroxyl group of a hydroxyl group-containing monomer described below. Examples include mercury.

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

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

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

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

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

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

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

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

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

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

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

The content of the binder resin (G) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on 100 parts by mass of the colorant (A).
[Sensitizer (H)]
The photosensitive coloring composition of the present invention can contain a sensitizer (H).

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

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

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

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

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

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

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

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

The content of the epoxy compound (I1) is preferably 0.5 to 50% by weight, more preferably 1 to 40% by weight based on 100% by weight of nonvolatile content of the photosensitive coloring composition.

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

Monofunctional oxetane compounds include, for example, (3-ethyloxetan-3-yl)methyl acrylate, (3-ethyloxetan-3-yl)methyl methacrylate, 3-ethyl-3-hydroxymethyloxetane, 3-ethyl-3- (2-ethylhexyloxymethyl)oxetane, 3-ethyl-3-(phenoxymethyl)oxetane, 3-ethyl-3-(2-methacryloxymethyl)oxetane, 3-ethyl-3-{[3-(triethoxy) silyl)propoxy]methyl}oxetane, and the like.

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

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

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

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

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

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

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

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

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

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

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

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

[Thiol chain transfer agent (J)]
The photosensitive coloring composition of the present invention can contain a thiol chain transfer agent (J). When the thiol-based chain transfer agent (J) is used in combination with the oxime-based photopolymerization initiator (D), thiyl radicals, which are less susceptible to polymerization inhibition by oxygen, are generated during radical polymerization after light irradiation, and the photosensitive coloring composition undergoes photopolymerization. Sensitivity is improved.
The thiol chain transfer agent (J) is preferably a polyfunctional thiol having two or more thiol groups (SH groups), more preferably a polyfunctional thiol having four or more. As the number of functional groups increases, it becomes easier to photocure from the surface of the film to the deepest part.

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

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

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

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

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

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

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

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

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

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

Examples of triazine compounds include 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4, 6-bis(2,4-dimethylphenyl)-1,3,5-triazin-2-yl]-5
-[3-(dodecyloxy)-2-hydroxypropoxy]phenol, 2-(2,4-dihydroxyphenyl)-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and ( Reaction product of 2-ethylhexyl)-glycidic acid ester, 2,4-bis “2-hydroxy-4-butoxyphenyl”-6-(2,4-dibutoxyphenyl)-1,3,5-triazine, 2 -(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol, 2-(4,6-diphenyl-1,3,5-triazin-2-yl) -5-[2-(2-ethylhexanoyloxy)ethoxy]phenol, 2,4,6-tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine, etc. Can be mentioned.

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

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

Commercially available products include, for example, KEMISORB 10, 11, 11S, 12, 111 manufactured by Chemipro Kasei Co., Ltd., SEESORB 101, 107 manufactured by Shipro Kasei Co., Ltd., ADEKA STAB 1413 manufactured by ADEKA Co., Ltd., and UV-12 manufactured by Sun Chemical Co., Ltd. It will be done.

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

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

[Antioxidant (M)]
The photosensitive coloring composition of the present invention can contain an antioxidant (M).

The antioxidant (M) prevents yellowing caused by oxidation of the oxime photopolymerization initiator (D) and thermosetting compound (I) in the photosensitive coloring composition 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 it is necessary to increase the amount of the oxime photopolymerization initiator (D) or to heat cure the composition. If the cured film is mixed with a chemical compound, the cured film tends to yellow. Therefore, by including an antioxidant, yellowing of the cured film due to oxidation during the heating process is prevented. The antioxidant (M) is preferably a compound that does not contain a halogen atom.

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

The hindered phenolic antioxidant is, for example, 1,3,5-tris(3,5-di-t-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H ,3H,5H)-trione, 1,1,3-tris-(2'-methyl-4'-hydroxy-5'-t-butylphenyl)-butane, 4,4'-butylidene-bis-(2- t-butyl-5-methylphenol), stearyl 3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, pentaerythritol tetrakis [3-(3,5-di-t-butyl-4 -hydroxyphenyl)propionate, 3,9-bis[2-[3-(3-t-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl]-2,4,8 , 10-tetraoxaspiro[5.5]undecane, 1,3,5-tris(3,5-di-t-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene, 1,3 ,5-tris(3-hydroxy-4-t-butyl-2,6-dimethylbenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 2,2' -Methylenebis(6-t-butyl-4-ethylphenol), 2,2'-thiodiethylbis-(3,5-di-t-butyl-4-hydroxyphenyl)-propionate, N,N-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamamide), i-octyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate, 4,6-bis (dodecylthiomethyl)-o-cresol, calcium salt of 3,5-di-t-butyl-4-hydroxybenzylphosphonic acid monoethyl ester, 4,6-bis(octylthiomethyl)-o-cresol, bis[ 3-(3-Methyl-4-hydroxy-5-t-butylphenyl)propionic acid] ethylenebisoxybisethylene, 1,6-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) - Examples include phenol.

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

Examples of hindered amine antioxidants include tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl)-1,2,3,4-butanetetracarboxylate, tetrakis(2,2,6,6 -tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis(1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, bis(2,2,6,6 -tetramethyl-4-piperidyl) sebacate, bis(1-undecanoxy-2,2,6,6-tetramethylpiperidin-4-yl)carbonate, 1,2,2,6,6-pentamethyl-4-piperidyl methacrylate , 2,2,6,6-tetramethyl-4-piperidyl methacrylate, polycondensate of dimethyl succinate and 1-(2-hydroxyethyl)-4-hydroxy-2,2,6,6-tetramethylpiperidine , poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl) ) imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol and 3, Ester of 5,5-trimethylhexanoic acid, N,N'-4,7-tetrakis[4,6-bis{N-butyl-N-(1,2,2,6,6-pentamethyl-4-piperidyl) amino}-1,3,5-triazin-2-yl]-4,7-diazadecane-1,10-diamine, bis(2,2,6,6-tetramethyl-1-(octyloxy) decanedioate) -4-piperidinyl) ester, reaction product of 1,1-dimethylethyl hydroperoxide and octane, bis(1,2,2,6,6-pentamethyl-4-pyriperidyl)[[3,5-bis(1, 1dimethylethyl)-4-hydroxyphenyl]methyl]butyl malonate methyl 1,2,2,6,6-pentamethyl-4-pyriperidyl sebacate, poly[[6-morpholino-s-triazine-2,4 -diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino]], 2, 2,6,6-tetramethyl-4-piperidyl-C12-21 and C18 unsaturated fatty acid ester, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-1,6- Hexamethylene diamine, 2-methyl-2-(2,2,6,6-tetramethyl-4-piperidyl)amino-N-(2,2,6,6-tetramethyl-4-piperidyl)propionamide, etc. Can be mentioned.

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

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

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

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

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

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

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

[Leveling agent (N)]
The photosensitive coloring composition of the present invention can contain a leveling agent (N). This further improves the wettability and drying properties for the substrate during coating.

Examples of the leveling agent (N) include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, anionic surfactants, and amphoteric surfactants.

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

Commercially available products include, for example, BYK-300, 306, 310, 313, 315N, 320, 322, 323, 330, 331, 333, 342, 345, 346, 347, 348, 349, 370, 377, manufactured by BYK Chemie. 378, 3455, UV3510, 3570, FZ-7002, 2110, 2122, 2123, 2191, 5609 manufactured by Dow Corning Toray, X-22-4952, X-22-4272, X- manufactured by Shin-Etsu Chemical Co., Ltd. 22-6266, KF-351A, KF-354L, KF-355A, KF-945, KF-640, KF-642, KF-643, X-22-4515, KF-6004, KP-341, etc.

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

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

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

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

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

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

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

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

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

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

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

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

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

Storage stabilizers (O) include, for example, quaternary ammonium chlorides such as benzyl trimethyl chloride and diethyl hydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, t-butylpyrocatechol, tetraethylphosphine, and tetraphenyl. Examples include organic phosphines and phosphites.

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

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

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

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

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

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

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

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

[Content of specific metal elements]
The photosensitive coloring composition of the present invention has a total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr (hereinafter also referred to as specific metal elements) contained in the photosensitive coloring composition of 500 The mass is less than ppm.

When the photosensitive coloring composition has a total amount of specific metal elements within the above range, it has excellent dispersion stability and sensitivity even after storage over time. In addition, color filters made using photosensitive coloring compositions in which the total amount of specific metal elements is within the above range have excellent heat resistance, generate less foreign matter even when heated, and do not reduce brightness due to backlighting. It can be suppressed.

The total amount of specific metal elements contained in the photosensitive coloring composition is more preferably 300 mass ppm or less, particularly preferably 200 mass ppm or less. Further, the lower limit of the total amount of the specific metal element is not particularly limited, but is preferably 1 ppm or more by mass, and more preferably 5 ppm or more by mass. Within the above range, it is possible to obtain a photosensitive coloring composition that can reduce costs, have excellent storage stability, and form a color filter with less generation of foreign matter and less reduction in brightness.

The amount of each specific metal element contained in the photosensitive coloring composition is preferably 100 mass ppm or less, and more preferably 50 mass ppm or less.
Furthermore, among the specific metal elements, the content of Li, which has high reactivity with the oxime photopolymerization initiator (D), is preferably 30 mass ppm or less, more preferably 15 mass ppm or less. .

The method for reducing the specific metal element contained in the photosensitive coloring composition is not particularly limited, but since the specific metal element is contained in a large amount in the colorant (A), it is possible to remove the specific metal element from the colorant (A). It is preferable to do so. In addition, since it is also mixed in from the equipment for manufacturing the photosensitive coloring composition, it is also preferable to suppress the mixing from the equipment.

The method for reducing and removing the specific metal element contained in the colorant (A) is not particularly limited, and known methods can be used. For example, methods to avoid contamination from equipment during the manufacturing process include methods described in JP-A No. 2010-83997, JP-A No. 2018-36521, and the like. For example, methods for removing colorant (A) are described in JP-A-7-198928, JP-A-8-333521, JP-A-2009-7432, JP-A-2010-83997, etc. Examples include the methods described. Among these, a method in which the colorant (A) is washed with water having a low content of specific metal elements, such as ion-exchanged water, is preferred.

The method for washing the colorant (A) is not particularly limited, and any known method can be used. For example, the synthesized colorant (A) is placed in a container containing ion-exchanged water and stirred. After stirring for a certain period of time, it is filtered using a filter press to separate the colorant (A) and ion-exchanged water. This operation is repeated until the amount of the specific metal element reaches a desired value. It is preferable to perform the washing while heating. Thereafter, the colorant (A) is dried with hot air and pulverized.

The content of the specific metal element can be measured by inductively coupled plasma emission spectroscopy (ICP).

In the photosensitive coloring composition of the present invention, it is preferable that the content of metal elements other than the specific metal elements is also reduced from the viewpoint of storage stability, suppression of foreign matter generation, and suppression of reduction in brightness. Examples of metals other than the specific metal elements include Mn, Cs, Ti, Co, Ni, Si, and Pd.

[Water content]
The photosensitive coloring composition of the present invention has a water content of 2.0% by mass or less.

A photosensitive coloring composition with a water content within the above range has excellent dispersion stability and sensitivity even after storage over time.

The content of water contained in the photosensitive coloring composition is preferably 1.8% by mass or less, more preferably 1.6% by mass or less. Further, the lower limit of the water content is preferably as small as possible, and there is no particular restriction on the lower limit. Within the above range, the dispersion stability and sensitivity are excellent even after storage over time.

The method for controlling the water content is not particularly limited, and any known method can be used. Examples include a method of producing a photosensitive coloring composition while blowing dry air, an inert gas, or a mixed gas thereof, and a method of adding molecular sieve to dehydrate the composition after production. Among these, a method of manufacturing while blowing dry air or inert gas is preferred.

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

Although the mechanism by which the photosensitive coloring composition having the above structure can solve the problems of the present invention is not clear, it is speculated as follows.

It is presumed that by reducing the amount of the specific metal element and the amount of water, the ionization of the specific metal element was suppressed and the reaction with the oxime photopolymerization initiator during storage over time was suppressed. It is also assumed that the dispersion resin having an acidic group forms a salt with the ionized specific metal element, thereby suppressing the reaction with the oxime photopolymerization initiator during storage over time.

[Content of zirconium compound]
In the photosensitive coloring composition of the present invention, it is preferable that the content of the zirconium compound contained in the photosensitive coloring composition is 800 mass ppm or less.

The zirconium compound is obtained by pulverizing the dispersion media used in the dispersion machine when dispersing the colorant (A), and these pulverized substances serve as nuclei and generate foreign matter when heated. Therefore, it is preferable to reduce the content of the zirconium compound contained in the photosensitive coloring composition.

When the content of the zirconium compound is within the above range of the photosensitive coloring composition, a color filter with less generation of foreign matter upon heating can be obtained.

The content of the zirconium compound contained in the photosensitive coloring composition is more preferably 700 mass ppm or less, particularly preferably 600 mass ppm or less. Further, the lower limit of the zirconium compound is not particularly limited, but is preferably 1 ppm or more by mass, more preferably 5 ppm or more by mass. If it is within the above range, the cost can be reduced and a color filter with less foreign matter generated by heating can be obtained.

The method for reducing the content of the zirconium compound is not particularly limited, and any known method can be used. Examples include a dispersion method using a dispersion machine without dispersion media, a method of suppressing wear by lowering the shear during dispersion or shortening the dispersion time, and a method of performing centrifugation after dispersion.

The content of zirconium compounds can be measured by inductively coupled plasma emission spectroscopy (ICP).

[Method for producing photosensitive coloring composition]
The photosensitive coloring composition of the present invention can be prepared by adding, for example, a colorant (A), a dispersion resin having an acidic group (B1), a copper salt of a quinophthalone compound having a sulfo group (E), an organic solvent (Q), etc. Then, a dispersion is produced by performing a dispersion treatment under a dry inert gas. Thereafter, under dry inert gas, the polymerizable compound (C), oxime photopolymerization initiator (D), binder resin (G), etc. are added to the dispersion and mixed. Note that the timing of blending each material is arbitrary. It is also preferable to work in a humidity-controlled area to avoid contamination with water from the atmosphere.

Examples of the dispersing machine that performs the dispersion treatment include a two-roll mill, a three-roll mill, a ball mill, a horizontal sand mill, a vertical sand mill, an annular bead mill, and an attritor.

The average dispersed particle size (secondary particle size) of the pigment in the dispersion is preferably 30 to 200 nm, more preferably 40 to 200 nm. When the particle size is appropriate, it is easy to obtain a photosensitive coloring composition with high dispersion stability.

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

The photosensitive coloring composition is filtered using a sintered filter or a membrane filter to remove coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm or more, and mixed dust. It is preferable to remove. The photosensitive coloring composition of the present invention preferably does not substantially contain particles of 0.5 μm or more, and more preferably does not contain particles of 0.3 μm or less.

<Color filter>
The color filter of the present invention includes 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 colorant (A) used. Moreover, the color filter can have a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment instead of or in addition to the color filter segments.
Examples of the substrate include a transparent substrate and a reflective substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective base material include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

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

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

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

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

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

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

<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, published by Kogyo Chosenkai Co., Ltd., 1994) can be mentioned.
For the definition of image display devices and details of each image display device, see, for example, "Electronic Display Devices (written by Akio Sasaki, published by Kogyo Chosenkai Co., Ltd., 1990)" and "Display Devices (written by Junaki Ibuki, published by Sangyo Tosho. Co., Ltd., published in 1989).

<Solid-state 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 device consisting of a plurality of photodiodes, polysilicon, etc. that constitute the light-receiving area of the solid-state image sensor (CCD image sensor, CMOS image sensor, etc.) on a base material. It has an electrode, has a light-shielding film on the photodiode and transfer electrode with an opening only at the light-receiving part of the photodiode, 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 a color filter on the device protective film. In addition, there may be a configuration in which a light condensing means (for example, a microlens, etc., the same applies hereinafter) is provided on the device protective film and below the color filter (on the side closer to the base material), a configuration in which the condensing means is provided on the color filter, etc. It 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 into, for example, a lattice shape by partition walls. In this case, the partition wall preferably has a low refractive index for each colored pixel.
The imaging device including the solid-state imaging device of the present invention can be used not only for digital cameras and electronic devices having an imaging function (mobile phones, smartphones, etc.), but also for in-vehicle cameras and surveillance cameras.

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

Prior to Examples, each measurement method will be explained.

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

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

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

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

(Measurement of content of specific metal elements)
The contents of Li, Na, K, Mg, Ca, Fe, Al, and Cr contained in the photosensitive coloring composition were measured using an ICP emission spectrometer (ICPE-9800 manufactured by Shimadzu Corporation).

(Water content measurement)
The content of water contained in the photosensitive coloring composition was measured using a Karl Fischer titrator (volume titration type water measuring device KF-06 model manufactured by Mitsubishi Chemical Corporation).

(Measurement of zirconium compound content)
Using an ICP mass spectrometer (ICPMS-2030 manufactured by Shimadzu Corporation), the content in terms of zirconium concentration contained in the photosensitive coloring composition was measured.

<Production of colorant (A)>
(Fine colorant (A-1))
A 300 mL flask was charged with 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 59 parts of bromine. The temperature was raised to 130°C over 40 hours, taken out in water, and filtered. The average number of halogen atoms in one molecule was 12.71, of which the average number of bromine atoms was 10.22 and chlorine atoms. A halogenated zinc phthalocyanine compound having an average number of 2.49 was obtained.
100 parts of the halogenated zinc phthalocyanine compound, 1,200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 70° C. for 6 hours. Next, this kneaded material was poured into 3,000 parts of ion-exchanged water, stirred for 1 hour while heating to 70° C., and then filtered (washing step). After repeating this washing step three times, it was dried at 80° C. for a day and night to obtain a finely divided colorant (A-1).

(Fine colorant (A-2))
According to the synthesis method of Example 8 of JP-A-2012-226110, a quinophthalone compound represented by the following chemical formula (22) was obtained.
100 parts of the quinophthalone compound represented by chemical formula (22), 700 parts of sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80° C. for 6 hours. Next, this mixture was poured into 3,000 parts of ion-exchanged water, stirred for 1 hour while heating to 70°C, and then filtered (washing step). After repeating this washing step three times, it was dried at 80° C. for a day and night to obtain a finely divided colorant (A-2).
Chemical formula (22)

(Fine colorant (A-3))
A 300 mL flask was charged with 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 59 parts of bromine. The temperature was raised to 130°C over 40 hours, taken out in water, and filtered. The average number of halogen atoms in one molecule was 12.71, of which the average number of bromine atoms was 10.22 and chlorine atoms. A halogenated zinc phthalocyanine compound having an average number of 2.49 was obtained.
100 parts of the halogenated zinc phthalocyanine compound, 1200 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.), and kneaded at 70° C. for 6 hours. Next, this kneaded product was poured into 3,000 parts of tap water, stirred at room temperature for 1 hour, and then filtered. Thereafter, it was dried at 80° C. for a day and night to obtain a finely divided coloring agent (A-3).

(Fine colorant (A-4))
According to the synthesis method of Example 8 of JP-A-2012-226110, a quinophthalone compound represented by the above chemical formula (22) was obtained.
100 parts of the quinophthalone compound represented by chemical formula (22), 700 parts of sodium chloride, and 180 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 80° C. for 6 hours. Next, this kneaded product was poured into 3,000 parts of tap water, stirred at room temperature for 1 hour, and then filtered. Thereafter, it was dried at 80° C. for a day and night to obtain a finely divided coloring agent (A-4).

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

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

(Basic dispersion resin (B2-1) solution)
30 parts of methyl methacrylate, 30 parts of n-butyl methacrylate, 20 parts of hydroxyethyl methacrylate, and 13.2 parts of tetramethylethylenediamine were charged into a reaction apparatus equipped with a gas inlet pipe, a condenser, a stirring blade, and a thermometer, and the mixture was flushed with nitrogen. The mixture was stirred at 50° C. for 1 hour while purging the system 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 polymerization of the first block (B block). After 4 hours of polymerization, the polymerization solution was sampled and the nonvolatile content was measured, and it was confirmed that the polymerization conversion rate was 98% or more as calculated from the nonvolatile content.
Next, 61 parts of PGMAc and 20 parts of 1,2,2,6,6-pentamethylpiperidyl methacrylate (manufactured by Hitachi Chemical Co., Ltd., Fancryl FA-711MM) were added to this reactor. The reaction was continued by stirring while maintaining the temperature at 110° C. and nitrogen atmosphere. Two hours after adding 1,2,2,6,6-pentamethylpiperidyl methacrylate, 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 in terms of non-volatile content. % or more, and the reaction solution was cooled to room temperature to stop the polymerization. A basic dispersion resin (B2-1) that is diluted with PGMAc so that the nonvolatile content becomes 30% in nonvolatile content measurement, and has an amine value per nonvolatile content of 57 mgKOH/g and a number average molecular weight of 4,500 (Mn). A solution was obtained.

(Basic dispersion resin (B2-2) solution)
In a 500 mL round-bottomed 4-neck separable flask equipped with a condenser, an addition funnel, a nitrogen inlet, a mechanical stirrer, and a digital thermometer, 250 parts by mass of tetrahydrofuran (THF) and 5.81 parts of dimethylketenemethyltrimethylsilyl acetal as an initiator were added. Parts by mass were added via the addition funnel, and the mixture was sufficiently purged with nitrogen. Using a syringe, 0.5 parts by mass of a 1 mol/L acetonitrile solution of tetrabutylammonium m-chlorobenzoate as a catalyst was injected, and 19.7 parts by mass of 2-hydroxyethyl methacrylate, a blocking monomer having solvent affinity, was added. , 7.5 parts by mass of 2-ethylhexyl methacrylate, 12.9 parts by mass of n-butyl methacrylate, 10.7 parts by mass of benzyl methacrylate, and 30.9 parts by mass of methyl methacrylate were added using an addition funnel for 60 minutes. It dripped. The temperature was kept below 40°C by cooling the reaction flask with an ice bath. After 1 hour, 18.3 parts by mass of dimethylaminopropyl methacrylamide, which is a monomer for a colorant adsorption functional block, was added dropwise over 20 minutes. After reacting for 1 hour, 1 part by mass of methanol was added to stop the reaction. The obtained block copolymer THF solution was reprecipitated in hexane, and purified by filtration and vacuum drying.
Subsequently, 15.0 parts by mass of the obtained block copolymer was dissolved in 35 parts by mass of PGMAc in a 100 mL round bottom flask, and 1.1 parts by mass of phenylphosphinic acid (dimethylaminopropyl methacrylamide), which is a salt forming component, was dissolved in 35 parts by mass of PGMAc. The mixture was stirred at a reaction temperature of 30° C. for 20 hours, and adjusted by adding PGMAc to obtain a basic dispersion resin (B2-2) solution with a nonvolatile content of 30%.

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

<Production of metal salt (E) of quinophthalone compound having sulfo group>
(Copper salt of quinophthalone compound having sulfo group (E-1))
The quinophthalone compound C.I. I. Pigment Yellow 138 (“Paliotol Yellow K0960-HD” manufactured by BASF Japan) was dissolved in 300 parts of 101% sulfuric acid and stirred at 70° C. for 8 hours to perform a sulfonation reaction. The end point of the reaction was determined by measuring the spectrum of the sulfuric acid solution, and was defined as the point at which no change in the spectrum was observed. Next, this reaction solution was poured into 3,000 parts of ice water, and the precipitate was filtered off, washed with water, and dried at 80°C to obtain a quinophthalone compound having a sulfo group.
Next, 10 g of a quinophthalone compound having a sulfo group was added to 500 parts of water and stirred at 25° C. for 2 hours to redisperse the mixture. Next, 4.8 parts of copper (II) sulfate pentahydrate was gradually added to this solution, and the mixture was reacted at 60° C. for 2 hours. The reaction product was filtered, poured into ion-exchanged water, stirred for 1 hour while heating at 70°C, and then filtered (washing step). After repeating this washing step three times, it was dried at 80° C. to obtain a copper salt (E-1) of a quinophthalone compound having a sulfo group represented by the following chemical formula (23).
Chemical formula (23)

<Manufacture of binder resin (G)>
(Binder resin (G-1) solution)
100 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, the temperature was raised to 80°C, the inside of the reaction vessel was replaced with nitrogen, and then added dropwise. From the tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) A mixture of 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain a resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. A binder resin (G-1) solution was prepared. The weight average molecular weight (Mw) was 26,000.

(Binder resin (G-2) solution)
100 parts of cyclohexanone was charged into a reaction vessel equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device in a separable 4-necked flask, the temperature was raised to 80°C, the inside of the reaction vessel was replaced with nitrogen, and then added dropwise. From the tube, 20 parts of methacrylic acid, 20 parts of paracumylphenol ethylene oxide modified acrylate (Aronix M110 manufactured by Toagosei Co., Ltd.), 45 parts of methyl methacrylate, 8.5 parts of 2-hydroxyethyl methacrylate, and 2,2-azobisiso A mixture of 1.33 parts of butyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain a copolymer resin solution. Next, the entire amount of the obtained copolymer solution was stirred while stopping the nitrogen gas supply and injecting dry air for 1 hour, and then cooled to room temperature. A mixture of 6.5 parts of MOI), 0.08 parts of dibutyltin laurate, and 26 parts of cyclohexanone was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain a resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content, and cyclohexanone was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. A binder resin (G-2) solution was prepared. The weight average molecular weight (Mw) was 18,000.

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

(Binder resin (G-4) solution)
A separable flask equipped with a cooling tube was prepared as a reaction tank, and on the other hand, as a monomer dropping tank, 40 parts of dimethyl-2,2'-[oxybis(methylene)]bis-2-propenoate, 40 parts of methacrylic acid, and methacrylic acid were prepared. Prepare a well-stirred mixture of 120 parts of methyl, 4 parts of t-butyl peroxy 2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation), and 40 parts of PGMAc, and use it as a chain transfer agent dropping tank to add n-dodecanethiol. A mixture of 8 parts of PGMAc and 32 parts of PGMAc was prepared by thoroughly stirring and mixing.
After charging 200 parts of PGMAc into a reaction tank and replacing the atmosphere with nitrogen, the reaction tank was heated in an oil bath while stirring to raise the temperature of the reaction tank to 90°C. After the temperature of the reaction tank stabilized at 90°C, dropping was started from the monomer dropping tank and the chain transfer agent dropping tank. Each dropwise addition took 135 minutes while maintaining the temperature at 90°C. Sixty minutes after the dropwise addition was completed, the temperature was started to rise to 110° C. in the reaction tank. After maintaining the temperature at 110°C for 3 hours, a gas introduction tube was attached to the separable flask, and bubbling of a mixed gas of oxygen/nitrogen = 5/95 (volume ratio) was started. Next, 70 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis(4-methyl-6-t-butylphenol), and 0.8 parts of triethylamine were placed in a reaction tank, and the mixture was allowed to react at 110°C for 12 hours. Ta. After that, 150 parts of PGMAc was added and cooled to room temperature, and about 2 g of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content, and the nonvolatile content was 20% by mass in the resin solution synthesized earlier. PGMAc was added to obtain a binder resin (G-4) solution. The weight average molecular weight of the resin was 18,000, and the acid value per nonvolatile content was 2 mgKOH/g.

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

(Binder resin (G-6) solution)
150 parts of PGMAc was introduced into a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and after changing the atmosphere inside the flask from air to nitrogen, the temperature was raised to 100°C, and 70.0 parts of benzyl methacrylate was added. 5 parts (0.40 mol) of azobisisobutyronitrile, 43.0 parts (0.5 mol) of methacrylic acid, 22.0 parts (0.10 mol) of dicyclopentanyl methacrylate, and 136 parts of PGMAc. A solution containing 3.6 parts was added dropwise from the dropping funnel to the flask over 2 hours, and the mixture was further stirred at 100°C for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate [0.25 mol, (50 mol % based on the carboxyl group of methacrylic acid used in this reaction)] and 0 parts of trisdimethylaminomethylphenol were added. .9 parts and 0.145 parts of hydroquinone were put into the flask, and the reaction was continued at 110°C for 6 hours to obtain a resin solution with an acid value of 79 mgKOH/g. After cooling to room temperature, about 2 parts of the resin solution was sampled and heated and dried at 180°C for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20% by mass. A binder resin (G-6) solution was prepared. The weight average molecular weight (Mw) was 13,000.

<Production of dispersion>
(Dispersion 1)
After stirring and mixing the following raw materials so that they were uniform, they were dispersed for 3 hours using an Eiger mill ("Mini Model M-250 MKII" manufactured by Eiger Japan) using zirconia beads with a diameter of 0.5 mm, and then the pore size was Dispersion 1 was prepared by filtration with a 1.0 μm filter. The organic solvent (Q-1) is PGMAc.
Micronized colorant (A1-1): 10.0 parts Dispersion resin having acidic group (B1-1-2) solution: 10.0 parts Dispersion resin having basicity (B2-1) solution: 7.0 Part Binder resin (G-1) solution: 10.0 parts Organic solvent (Q-1): 63.0 parts

(Dispersions 2 to 7)
Dispersions 2 to 7 were prepared in the same manner as Dispersion 1, except that the raw materials and amounts listed in Table 1 were changed.

<Manufacture of photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition 1)
The following raw materials were charged into the container while blowing dry nitrogen gas, and the mixture was stirred for 2 hours. Thereafter, it was filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition 1.
Dispersion 1: 30.0 parts Dispersion 2: 12.5 parts Dispersion 3: 12.5 parts Polymerizable compound (C): 2.0 parts Oxime photopolymerization initiator (D1-1): 0.5 Parts Binder resin (G): 5.0 parts Sensitizer (H): 0.2 parts Thermosetting compound (I): 1.0 parts Thiol chain transfer agent (J): 0.1 part Polymerization prohibited Agent (K): 0.1 part Ultraviolet absorber (L): 0.1 part Antioxidant (M): 0.1 part Leveling agent (N): 1.5 part Storage stabilizer (O): 0. 1 part Organic solvent (Q): 34.3 parts

The obtained photosensitive coloring composition 1 was centrifuged using a centrifuge (himacCP-NX manufactured by Hitachi Koki Co., Ltd.).

Regarding the obtained photosensitive coloring composition 1, the content of the specific metal element, the content of water, and the content of the zirconium compound were measured.

[Examples 2 to 11, Comparative Examples 1 to 3]
(Photosensitive coloring compositions 2-11, 13-15)
Photosensitive coloring compositions 2 to 11 and photosensitive coloring compositions 2 to 11 were prepared in the same manner as in Example 1, except that photosensitive coloring composition 1 of Example 1 was changed to the raw materials and amounts listed in Table 2-1 and Table 2-2. Coloring compositions 13 to 15 were prepared, and the content of specific metal elements, water content, and zirconium compound content were measured.

[Example 12, Comparative Example 4]
(Photosensitive coloring compositions 12, 16)
Photosensitive coloring composition 12 of Example 12 was prepared in the same manner as photosensitive coloring composition 1 of Example 1, except that centrifugation was not performed. In addition, photosensitive coloring composition 1 of Comparative Example 4
Sample No. 6 was prepared in the same manner as photosensitive coloring composition 1 of Example 1, except that dry nitrogen gas was not blown into the photosensitive coloring composition.

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

[Polymerizable compound (C)]
(C-1): Aronix M-521 (manufactured by Toagosei Co., Ltd., acrylate with an acidic group) (C-2): KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd., lactone-modified acrylate)
(C-3): KAYARAD DPHA (manufactured by Nippon Kayaku Co., Ltd., mixture of dipentaerythritol hexaacrylate and dipentaerythritol pentaacrylate)
(C-4): The above solution of the polymerizable compound (C-4) having a urethane bond and the same amounts of each of (C-1) to (C-4) were mixed to obtain a polymerizable compound (C).

[Oxime-based photopolymerization initiator (D)]
(Compound (D1) represented by general formula (1))
(D1-1): Compound of the above chemical formula (15) (D1-2): Compound of the above chemical formula (16) (D1-3): Compound of the above chemical formula (17) (D1-4): Compound of the above chemical formula (17) Compound of chemical formula (18) (D1-5): Compound of chemical formula (19) described above (D1-6): Compound of chemical formula (20) described above

(Oxime-based photopolymerization initiator other than compound (D1) represented by general formula (1))
(D-1): IRGACURE OXE-01 (manufactured by BASF Japan, oxime-based photopolymerization initiation)
(D-2): IRGACURE OXE-04 (manufactured by BASF Japan, oxime photoinitiator)

[Other photopolymerization initiators (F)]
(F-1): Omnirad 369 (manufactured by IGM Resins, acetophenone-based photopolymerization initiator)
(F-2): Omnirad 907 (manufactured by IGM Resins, acetophenone-based photopolymerization initiator)

[Binder resin (G) solution]
Binder resin (G-1) to (G-6) solutions were mixed in the same amount to prepare a binder resin (G) solution.

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

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

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

[Polymerization inhibitor (K)]
(K-1): 4-Methylcatechol (K-2): Methylhydroquinone (K-3): t-butylhydroquinone Above, (K-1) to (K-3) were mixed in the same amount, This was used as a polymerization inhibitor (K).

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

[Antioxidant (M)]
(M-1): Pentaerythritol tetrakis [3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (M-2): Dioctadecyl 3,3-thiodipropanoate (M-3): Tris [2,4-di-(t)-butylphenyl]phosphine (M-4): Bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (M-5): p-octylphenyl salicylate The above (M-1) to (M-5) were mixed in the same amount to prepare an antioxidant (M).

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

[Storage stabilizer (O)]
(O-1): 2,6-bis(1,1-dimethylethyl)-4-methylphenol (O-2): Triphenylphosphine or more, equal amounts of (O-1) and (O-2) each The mixture was mixed to prepare a storage stabilizer (O).

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

<Evaluation of photosensitive coloring composition>
The obtained photosensitive coloring compositions 1 to 16 (Examples 1 to 12, Comparative Examples 1 to 4) were evaluated as follows. The evaluation results are shown in Table 3.

[Initial sensitivity evaluation]
The obtained photosensitive coloring composition was spin-coated onto a glass substrate using a spin coater so that the dry film thickness was 1.2 μm, and prebaked at 120° C. for 120 seconds. Next, after cooling this substrate to room temperature, it was exposed to ultraviolet light through a photomask using an ultra-high pressure mercury lamp. After that, this substrate was spray-developed using a sodium carbonate aqueous solution at 23°C, washed with ion-exchanged water, air-dried, and heat-treated at 230°C for 30 minutes in a clean oven to form a striped color on the substrate. formed a pixel.
The sensitivity of the photosensitive coloring composition was evaluated based on the minimum irradiation exposure amount at which the formed colored pixel pattern was completed according to the image dimensions of the photomask. 3 or more is practical.
5: Less than 50 mJ/cm ² 4: More than 50, less than 80 mJ/cm ^{2 3} : More than 80, less than 120 mJ/cm ² 2: More than 120, less than 150 mJ/cm ² 1: More than 150 mJ/cm ²

[Storage stability evaluation (1): Viscosity change rate]
The obtained photosensitive coloring composition was stored in a sealed container at 40° C. for one week, and the rate of change in viscosity before and after storage was calculated and evaluated using the following formula. The viscosity was measured using an E-type viscometer (“ELD-type viscometer” manufactured by Toki Sangyo Co., Ltd.) at 25° C. and at a rotation speed of 50 rpm. 2 or more is practical.
[Viscosity change rate over time] = | ([Initial viscosity] - [Viscosity over time]) / [Initial viscosity] | × 100
3: Change rate is less than 5% 2: Change rate is 5% or more and less than 10% 1: Change rate is 10% or more

[Storage stability evaluation (2): Sensitivity over time]
The obtained photosensitive coloring composition was stored in a sealed container at 40° C. for one week, and a pattern was created from the photosensitive coloring composition after storage under the same conditions as the initial sensitivity evaluation.
The width of the formed pattern was measured using a scanning line electron microscope and evaluated based on the following criteria. 2 or more is practical.
3: The pattern width using the photosensitive coloring composition after storage is in the range of 95 to 105% of the pattern width of the initial sensitivity evaluation. 2: The pattern width using the photosensitive coloring composition after storage is within the range of the initial sensitivity evaluation. Range of 90 to 110% of the pattern width 1: The pattern width using the photosensitive coloring composition after storage is less than 90% or more than 110% of the pattern width of the initial sensitivity evaluation

[Foreign substance evaluation]
The obtained photosensitive coloring composition was applied onto a glass substrate using a spin coater so that the chromaticity value of the coated film after heat treatment was y=0.60 using a C light source. Next, it was dried at 70°C for 20 minutes, exposed to light using a prescribed mask and an ultra-high pressure mercury lamp at an illumination intensity of 30mW/cm ² and 50mJ/cm ² , and spray developed with a sodium carbonate aqueous solution at 23°C, followed by ion exchange. Wash with water and air dry to form patterned pixels.
Thereafter, heat treatment was performed in an oven at 230° C. for 40 minutes, and the number of foreign particles on the glass substrate between pattern pixels was counted. For evaluation, surface observation was performed using a metallurgical microscope "BX60" (manufactured by Olympus Systems). The magnification was set to 500 times, and the number of foreign particles observable in five arbitrary fields of view was counted by integrating. 3 or more is practical.
5: Number of foreign objects is less than 5
4: The number of foreign objects is 5 or more and less than 10. 3: The number of foreign objects is 10 or more and less than 20. 2: The number of foreign objects is 20 or more and less than 50. 1: The number of foreign objects is 50 or more.

[Brightness evaluation]
The resulting photosensitive coloring composition was applied onto a glass substrate using a spin coater so that the chromaticity value of the coating film after heat treatment was y = 0.60 using a C light source, and dried at 70°C for 20 minutes. Ta. Next, exposure was performed using an ultra-high pressure mercury lamp at an illuminance of 30 mW/cm ² and 50 mJ/cm ² , and spray development was performed with a sodium carbonate aqueous solution at 23°C, followed by washing with ion-exchanged water, air drying, and heating at 230°C in an oven at 40°C. A heat treatment was performed for a minute to form a colored composition layer on the glass substrate.
Next, an overcoat agent was applied onto the colored composition layer using a spin coater, and the organic solvent was removed using a vacuum dryer. Thereafter, it was baked on a hot plate at 90°C for 2 minutes, and then heat-treated at 230°C for 60 minutes to obtain a brightness evaluation substrate.
The initial brightness of the obtained brightness evaluation substrate in the XYZ color system was measured using LVmicroZ (manufactured by Lambda Vision). Thereafter, after irradiating with ultraviolet rays for 200 hours using a 470 W/m ² xenon lamp, the brightness was measured again. The brightness change rate was determined from the following formula. 3 or more is practical.
Brightness change rate = | Brightness after 200 hours - Initial brightness | / Initial brightness x 100
5: Less than 3% 4: 3% or more, less than 5% 3: 5% or more, less than 10% 2: 10% or more, less than 15% 1: 15% or more

Claims (8)

A photosensitive coloring composition comprising a colorant (A), a dispersion resin (B), a polymerizable compound (C), and an oxime photopolymerization initiator (D),
The dispersion resin (B) includes a dispersion resin (B1) having an acidic group,
The total content of Li, Na, K, Mg, Ca, Fe, Al, and Cr contained in the photosensitive coloring composition is 500 mass ppm or less, and the water content is 2.0 mass% or less. A certain photosensitive coloring composition. Furthermore, the photosensitive coloring composition according to claim 1, wherein the content of the zirconium compound contained in the photosensitive coloring composition is 800 mass ppm or less. The photosensitive coloring composition according to claim 1 or 2, wherein the dispersion resin (B) further contains a dispersion resin (B2) having a basic group. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the oxime-based photopolymerization initiator (D) contains a compound (D1) represented by the following general formula (1).
General formula (1)


(In general formula (1), R ₁ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or Represents 2 to 20 heterocyclic groups.
R ₂ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₃ represents an alkyl group having 3 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.
R ₄ represents any monovalent substituent. n represents an integer from 0 to 3. ) The photosensitive coloring composition according to any one of claims 1 to 4, further comprising a copper salt (E) of a quinophthalone compound having a sulfo group. A color filter comprising a substrate and a filter segment formed using the photosensitive coloring composition according to any one of claims 1 to 5. A liquid crystal display device comprising the color filter according to claim 6. A solid-state image sensor comprising the color filter according to claim 6.