JP7404686B2 - Photosensitive coloring compositions, color filters and liquid crystal display devices - Google Patents

Description

The present invention relates to a photosensitive coloring composition used for manufacturing color filters used in color liquid crystal display devices, color solid-state image sensors, organic EL display devices, quantum dot display devices, electronic paper, and the like.

For color filters, it was necessary to shorten the takt time of the manufacturing process in order to improve productivity. Patent Document 1 discloses a photosensitive coloring composition containing an oxime ester initiator and a polyfunctional mercaptan compound.

Japanese Patent Application Publication No. 2006-10793

However, with conventional photosensitive coloring compositions, when color filter segments (hereinafter also referred to as pixels) are produced by photolithography under conditions of low exposure of 50 mJ/ ^m2 or less, the problem is that the straightness of the pattern is insufficient. Also, there was a problem that good adhesion with the substrate could not be obtained.

The present invention aims to provide a photosensitive coloring composition and a color filter that can form pixels with a good pattern shape and good adhesion to a substrate when manufactured at a low exposure dose of 50 mJ/m ² or less.

The photosensitive coloring composition of the present invention includes a colorant (A), a dispersant (B), a binder resin (C), a photopolymerizable compound (D), a photoinitiator (E),
The colorant (A) contains a diketopyrrolopyrrole red pigment (A1),
The photopolymerization initiator (E) is an oxime ester photopolymerization initiator [E1] whose maximum absorption peak wavelength on the longest wavelength side is less than 340 nm, and an oxime ester photopolymerization initiator [E1] whose maximum absorption peak wavelength on the longest wavelength side is 340 nm or more. Contains an ester photopolymerization initiator [E2].

When produced according to the present invention at a low exposure dose of 50 mJ/m ² or less, it is possible to provide a photosensitive coloring composition and a color filter that can form pixels with a good pattern shape and good adhesion to a substrate.

FIG. 1 is a schematic cross-sectional view of a liquid crystal display device.

Define terms used herein. "(meth)acryloyl", "(meth)acrylic", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" means "acryloyl and/or methacryloyl", "acrylic and/or methacrylic”, “acrylic acid and/or methacrylic acid”, “acrylate and/or methacrylate”, or “acrylamide and/or methacrylamide”. "C.I." is a color index (C.I.). Colorants include organic pigments, inorganic pigments, and dyes. The monomer is also called a monomer and is a compound containing a polymerizable unsaturated group. The polymerizable unsaturated group is a (meth)acrylyl group or a vinyl group.

The photosensitive coloring composition of the present invention includes a colorant (A), a dispersant (B), a binder resin (C), a photopolymerizable compound (D), a photoinitiator (E),
The colorant (A) contains a diketopyrrolopyrrole red pigment (A1),
The photopolymerization initiator (E) is an oxime ester photopolymerization initiator [E1] whose maximum absorption peak wavelength on the longest wavelength side is less than 340 nm, and an oxime ester photopolymerization initiator [E1] whose maximum absorption peak wavelength on the longest wavelength side is 340 nm or more. Contains an ester photopolymerization initiator [E2].

Conventionally, when forming a color filter segment containing a diketopyrrolopyrrole red pigment (A1), photocuring is performed at a low exposure dose of 50 mJ/m2 or ^less to improve productivity (shortening takt time), resulting in photosensitive coloring. The curing of the composition was insufficient, and the straightness of the outer periphery of the pixel after development was insufficient. Therefore, by using a oxime ester photopolymerization initiator [E1] and an oxime ester photopolymerization initiator [E2] that have different wavelength ranges where the photosensitivity is highest, a wide range of light source wavelengths can be used for photocuring, so the pattern shape It is possible to form a pixel with good adhesion to the substrate.

<Colorant (A)>
Colorants (A) include organic pigments, inorganic pigments, and dyes.
The colorant (A) contains a diketopyrrolopyrrole red pigment (A1). The diketopyrrolopyrrole red pigment (A1) is, for example, C.I. I. Pigment Red 254, 255, 264, 270, 272, 283, 291, a pigment represented by the following general formula (4), and the like. Among these, C. I. Pigment Red 254, 291, a pigment represented by the following general formula (4), is preferred.

General formula (4)

In the general formula (4), ~12 alkyl groups, phenyl groups that may have substituents, -CF ₃ , -OR ¹ , -SR ² , -N(R ³ )R ⁴ , -COOR ⁵ , -CONH ₂ , -CONHR ⁶ , -CON(R ⁷ )R ⁸ , -SO ₂ NH ₂ , -SO ₂ NHR ⁹ , or -SO ₂ N(R ¹⁰ )R ¹¹ , and R ¹ to R ¹¹ each independently represent the number of carbon atoms. It is an alkyl group of 1 to 12, a phenyl group which may have a substituent, or an aralkyl group which may have a substituent. However, A and B do not become hydrogen atoms at the same time. Further, X is never A and B is a hydrogen atom, and X is B and A is never a hydrogen atom.

The alkyl group having 1 to 12 carbon atoms may be linear or branched, for example, methyl group, ethyl group, propyl group, isopropyl group, butyl group, sec-butyl group, tert-butyl group, pentyl group, hexyl group. group, heptyl group, octyl group, decyl group, dodecyl group, 1,5-dimethylhexyl group, 1,6-dimethylheptyl group, 2-ethylhexyl group and the like.

The phenyl group which may have a substituent is, for example, an alkyl group having 1 to 4 carbon atoms, a trifluoromethyl group, a halogen atom, a nitro group, a cyano group, a carbamoyl group, a sulfamoyl group, an alkoxyl group having 1 to 4 carbon atoms. Examples include phenyl groups having substituents such as groups. More specifically, phenyl group, p-methylphenyl group, 4-tert-butylphenyl group, p-nitrophenyl group, p-methoxyphenyl group, p-chlorophenyl group, 2,4-dichlorophenyl group, 3-carbamoyl group. Examples include phenyl group.

Aralkyl groups which may have substituents include, for example, benzyl group, 4-methylbenzyl group, 4-tert-butylbenzyl group, 4-methoxybenzyl group, 4-nitrobenzyl group, 2,4-dichlorobenzyl group etc.

In this specification, the pigment represented by the general formula (4) is represented by the following general formula (4-1), the following general formula (4-2), the following general formula (4-3), and the following general formula (4-4). It is preferable that it is one or more selected from the group consisting of. This further improves brightness and contrast, and makes it difficult for crystals to precipitate. Furthermore, R ¹² to R ¹⁴ in the general formulas (4-3) and (4-4) are an alkyl group having 4 or more carbon atoms, or a phenyl group which may have a substituent, to improve contrast and crystal precipitation. Preferable in terms of suppression. The effect of improving contrast and suppressing crystal precipitation is that pigment aggregation is suppressed by the steric hindrance effect of bulky substituents such as carboxamide groups having alkyl groups of 4 or more carbon atoms, phenyl groups, and t-butyl groups. I'm guessing. Further, when the pigments represented by the general formula (4-3) and the following general formula (4-4) have a carboxamide group, a phenyl group, or a t-butyl group, the color characteristics are further improved.

In the general formula (4-1), the general formula (4-2), the general formula (4-3), and the general formula (4-4), each X independently represents a chlorine atom or a bromine atom. Furthermore, in the general formulas (4-3) and (4-4), R ¹² to R ¹⁴ are each independently an alkyl group having 1 to 12 carbon atoms or a phenyl group which may have a substituent. be. R ¹³ and R ¹⁴ may form a ring.

<Organic pigment (A2)>
It is preferable that the colorant (A) further contains one or more pigments (A2) selected from the group consisting of a pigment represented by the following general formula (2) and a pigment represented by the following general formula (3).

General formula (2)

In general formula (2), R ₁ represents a halogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or an aryloxy group that may have a substituent. R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group that may have a substituent, and a phenyl group that may have a substituent.
X ₁ to X ₄ each independently represent a hydrogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a sulfo group , represents a halogen atom.

General formula (3)

In general formula (3), R ₄ represents a halogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, or an aryloxy group that may have a substituent. R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, and a phenyl group which may have a substituent.
X ₅ to X ₁₂ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a hydroxy group, a cyano group, a nitro group, or a halogen atom. A represents a direct bond or a divalent linking group. As the divalent linking group, an alkylene group which may have a substituent, -O-, -S-, -CO-, -SO ₂ -, -COO-, -CONH-, -SO ₂ NH- represent.

<Other pigments>
Examples of pigments and dyes that can be contained in the photosensitive coloring composition of this specification are listed below. Note that the following examples include pigments that can be used in areas other than the red filter segment of the color filter.

The red pigment is, 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, 256, 257, 258, 259, 260, 262, 263, 265, 266, 267, 268, 269, 271, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 284, 285, 286, 287, 295, etc. Among these, from the viewpoint of pixel heat resistance, light resistance, and transmittance, C. I. Pigment Red 48:1, 122, 177, 224, 242, 269, 295 are preferred; I. Pigment Red 177 and 295 are more preferred.

Also, C. I. An orange pigment or a yellow pigment such as Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73 can be used in combination.

The blue pigment is, for example, 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, 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, from the viewpoint of pixel heat resistance, light resistance, and transmittance, C. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6 are preferred; I. Pigment Blue 15:6 is more preferred. A violet pigment can be used in combination with the blue photosensitive coloring composition.

The purple pigment is, for example, 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, from the viewpoint of pixel heat resistance, light resistance, and transmittance, C. I. Pigment Violet 19 or 23 is preferred, and C.I. I. Pigment Violet 23 is more preferred.

Green pigments 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 etc. are mentioned. Among these, from the viewpoint of transmittance, C. I. Pigment Green 36, 58, 59, 62 or 63 is preferred.
Moreover, a yellow pigment can be used in combination with the green photosensitive coloring composition.

Yellow pigments 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 and the like. Among these, C. I. Pigment Yellow 138, 139, 150, 185, 231, and 233 are preferred.

The cyan coloring composition for forming the cyan filter segment is, for example, C.I. I. Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, 16, and 81.

The magenta coloring composition for forming the magenta filter segment includes, for example, C.I. I. Pigment Violet 1, 19, C. I. Pigment Red 144, 146, 177, 169, 81 and the like. In addition. The magenta color composition can be used in combination with a yellow pigment.

Inorganic pigments include, for example, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine blue, deep blue, chromium oxide green, cobalt green, amber, Examples include synthetic iron black.

<Refining of pigments>
Among the colorants (A), the organic pigment is preferably mixed with other raw materials after being subjected to a finer treatment. Examples of the method for the micronization treatment include wet grinding, dry grinding, and solution precipitation. 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 organic pigment after the micronization treatment is preferably 10 to 80 nm, more preferably 15 to 70 nm. Appropriate particle size further improves dispersibility and further improves the contrast ratio of the coating. Note that the average primary particle diameter is the average value of about 20 particles arbitrarily selected from an enlarged image of a TEM (transmission electron microscope). Note that if the particle has a vertical axis length and a horizontal axis length, the vertical axis length is used.

In the salt milling process, a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent is processed in a batch or continuous manner using a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. This is a process in which the mixture is mechanically kneaded using a type kneader while being heated, and then 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, and sodium sulfate. Among these, 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 both treatment efficiency and production efficiency.

The water-soluble organic solvent wets the pigment and the water-soluble inorganic salt. A water-soluble organic solvent is a compound that dissolves (mixes) in water and does not substantially dissolve the water-soluble inorganic salt. The water-soluble organic solvent is preferably a high boiling point solvent with a boiling point of 120° C. or higher, since it is difficult to volatilize due to the temperature increase during salt milling. Examples of water-soluble organic solvents include 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, Triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. Can be mentioned. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by weight, more preferably 50 to 500 parts by weight, per 100 parts by weight of the pigment.

Resin can be added as needed during the salt milling process. Examples of the resin include natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature, insoluble in water, and more preferably partially soluble in a water-soluble organic solvent. The amount of resin used is preferably 5 to 200 parts by weight per 100 parts by weight of the pigment.

<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 dye derivatives and lake pigments obtained by turning dyes into lakes.

In addition, dyes include acid dyes having acidic groups such as sulfonic acid and carboxylic acid; in the case of direct dyes, inorganic salts of acid dyes; acid dyes, quaternary ammonium salt compounds, tertiary amine compounds, secondary amine compounds, Or a salt-forming compound with a primary amine compound; a salt-forming compound such as a resin component having these amino groups and an acidic dye. A salt-forming compound of an acidic dye and a compound having an onium base is also preferable because it has excellent fastness. Note that the compound having an onium base is preferably a resin having a cationic group in the side chain.

Examples of the basic dye include salt-forming compounds with organic acids, perchloric acid, or metal salts thereof. Among the salt-forming compounds, salt-forming compounds of basic dyes are preferred because they have excellent resistance to various types and compatibility with pigments.

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 dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, and rhodamine dyes. 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, Quinophthalone dyes, phthalocyanine dyes, and subphthalocyanine dyes are preferred, and xanthene dyes, cyanine dyes, triphenylmethane dyes, anthraquinone dyes, dipyrromethene dyes, and phthalocyanine dyes are more preferred. The specific structure of dyes can be found in the ``New Edition Dye Handbook'' (edited by the Organic Synthetic Chemistry Society; Maruzen, 1970), ``Color Index'' (The Society of Dyers and Colourists), and ``Pigment Handbook'' (edited by Okawara et al.; Kodansha, 1986). etc. are listed.

<Dispersion aid>
The photosensitive coloring composition of the present invention can contain a dye derivative as a dispersion aid.

<Dye derivative>
A dye derivative is a compound having an acidic group, a basic group, a neutral group, etc. in an organic dye residue. Dye derivatives include, for example, compounds having acidic substituents such as sulfo groups, carboxy groups, or phosphoric acid groups, as well as amine salts thereof, sulfonamide groups, or basic substituents such as tertiary amino groups at the terminals. Examples include compounds having a neutral substituent such as a phenyl group or a phthalimide alkyl group.
Examples of organic pigments include diketopyrrolopyrrole red pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazine indigo pigments, triazine pigments, benzimidazolone pigments, and benzo pigments. Examples include indole pigments such as isoindole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, and azo pigments such as azo, disazo, and polyazo. .

Specifically, diketopyrrolopyrrole dye derivatives include JP-A No. 2001-220520, WO 2009/081930 pamphlet, WO 2011/052617 pamphlet, WO 2012/102399 pamphlet, JP 2017-156397 pamphlet, and phthalocyanine-based dye derivatives. Pigment derivatives are disclosed in JP-A No. 2007-226161, WO2016/163351 pamphlet, JP-A-2017-165820, and Patent No. 5753266. Anthraquinone-based pigment derivatives are described in JP-A-63-264674 and JP-A-09-09. -272812, JP 10-245501, JP 10-265697, JP 2007-079094, WO2009/025325 pamphlet, quinacridone dye derivatives, JP 48-54128, JP-A-03-9961, JP-A 2000-273383, dioxazine dye derivatives, JP-A 2011-162662, thiazine indigo dye derivatives, JP-A 2007-314785, triazine dye derivatives are JP-A-61-246261, JP-A-11-199796, JP-A 2003-165922, JP-A 2003-168208, JP-A 2004-217842, and JP-A 2007-314681. , benzisoindole dye derivatives are disclosed in JP-A No. 2009-57478, and quinophthalone-based dye derivatives are described in JP-A Nos. 2003-167112, 2006-291194, 2008-31281, and 2012. -226110, naphthol dye derivatives, JP 2012-208329, JP 2014-5439, azo dye derivatives, JP 2001-172520, JP 2012-172092, acidic The substituent is described in JP-A No. 2004-307854, and the basic substituent is described in JP-A-2002-201377, JP-A 2003-171594, JP-A 2005-181383, and JP-A 2005-213404. Mention may be made of the dye derivatives described. In addition, in these documents, the dye derivative is sometimes described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply a compound. A compound having a substituent such as a neutral group has the same meaning as a dye derivative.

The dye derivatives can be used alone or in combination of two or more.

The content of the dye derivative is preferably 1 to 100 parts by weight, more preferably 3 to 70 parts by weight, and even more preferably 5 to 50 parts by weight, based on 100 parts by weight of the colorant (A).

By adding a pigment derivative to the colorant (A) and performing a pigmentation treatment such as acid pasting, acid slurry, dry milling, salt milling, and solvent salt milling, the pigment derivative is adsorbed on the pigment surface and the pigment derivative is The primary particles of the pigment can be made finer than when it is not added.

By adding a pigment derivative to the colorant (A) and performing a dispersion treatment such as two-roll, triple-roll, or wet dispersion using beads, the pigment derivative is adsorbed to the pigment surface and the pigment surface becomes polar and resin-type. Adsorption of dispersants is promoted, compatibility with pigments, dye derivatives, resin-type dispersants, solvents, and other additives is improved, and dispersion stability and viscosity over time are improved when used as colored compositions or colored curable compositions. Improved stability. In addition, due to improved compatibility, the coating film has excellent stability over time when the colored curable composition is applied to a glass substrate, etc., and the waiting time from application of the colored curable composition to exposure (PCD: Post Coating) The stability and characteristic dependence of the pattern shape on the waiting time from exposure to heat treatment (PED: Post Exposure Delay) and the line width sensitivity stability are improved. Furthermore, since the surface of the pigment is adsorbed and coated with the pigment derivative and the resin-type dispersant, it is possible to suppress crystal precipitation due to aggregation and sublimation of the pigment when the coating film is heated and baked. Furthermore, variations in development time and development residues are also suppressed.

<Dispersant (B)>
In the photosensitive coloring composition of the present invention, a known resin-type dispersant can be used as the dispersant (B). The resin-type dispersant has a colorant affinity site that has the property of adsorbing to the added colorant and a site that is compatible with the colorant carrier, and has a colorant affinity site that has the property of adsorbing to the added colorant and a site that is compatible with the colorant carrier. Any substance may be used as long as it has the function of stabilizing it, and specifically, urethane dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amines, etc. salts, polycarboxylic acid ammonium salts, polycarboxylic acid alkylamine salts, polysiloxanes, long-chain polyaminoamide phosphates, hydroxyl group-containing polycarboxylic acid esters, modified products thereof, poly(lower alkyleneimine) and free carboxyl groups. Oil-based dispersants such as amides and their salts formed by reaction with polyesters having Water-soluble resins such as acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide adducts, phosphate esters, etc. are used, and these These can be used alone or in combination of two or more.
Examples of polymeric dispersants having basic functional groups include nitrogen atom-containing graft copolymers and nitrogen atom-containing polymers having functional groups such as tertiary amino groups, quaternary ammonium bases, and nitrogen-containing heterocycles in their side chains. Examples include acrylic block copolymers and urethane polymer dispersants.

The resin-type dispersant is preferably used in an amount of about 3 to 200 parts by weight, and more preferably in an amount of about 5 to 100 parts by weight, based on 100 parts by weight of the colorant (A).

<Binder resin (C)>
The binder resin (C) is preferably a resin having a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm. Note that the transmittance is preferably 95% or more. In terms of curability, the binder resin includes, for example, thermoplastic resin, thermosetting resin, active energy ray curable resin, and the like. Note that the active energy ray-curable resin may be a thermoplastic resin or a thermosetting resin to which an active energy ray-reactive functional group is bonded. In terms of physical properties, the binder resin is preferably an alkali-soluble resin from the viewpoint of developability. Alkali solubility is for imparting development solubility in the alkaline development step during color filter production, and an acidic group is required.

<Thermoplastic resin>
Examples of the thermoplastic resin include acrylic resin, butyral resin, styrene-maleic acid copolymer, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, Examples include polyester resin, vinyl resin, alkyd resin, polystyrene resin, polyamide resin, rubber resin, cyclized rubber resin, celluloses, polyethylene (HDPE, LDPE), polybutadiene, and polyimide resin.
Examples of thermoplastic resins having alkali solubility include resins having acidic groups such as carboxyl groups and sulfone groups. Examples of thermoplastic resins having alkali solubility include acrylic resins having acidic groups, α-olefin/(anhydrous) maleic acid copolymers, styrene/styrene sulfonic acid copolymers, and ethylene/(meth)acrylic acid copolymers. , or isobutylene/(anhydrous) maleic acid copolymer. Among these, acrylic resins having acidic groups and styrene/styrene sulfonic acid copolymers are preferred from the viewpoint of improving developability, heat resistance, and transparency.

<Active energy ray-curable alkali-soluble resin>
The active energy ray-curable alkali-soluble resin has an ethylenically unsaturated group. The ethylenically unsaturated group can be introduced, for example, by methods (i) and (ii) shown below. Resin is three-dimensionally crosslinked by active energy rays, thereby 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 of obtaining an alkali-soluble resin by adding a carboxyl group-containing monomer to the epoxy group of the polymer and reacting the generated hydroxyl group with a polybasic acid anhydride can be mentioned.

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

Carboxyl group-containing monomers include, for example, (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-haloalkyl, alkoxyl, halogen, nitro, and cyano substituted products of (meth)acrylic acid. Examples include monocarboxylic acids such as.

Examples of the polybasic acid anhydride include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, and the like.

The monomers and polybasic acid anhydrides can be used alone or in combination of two or more.

Further, as a method similar to method (i), for example, a carboxyl group-containing monomer and other monomers are synthesized to produce a polymer. Next, there is a method in which an epoxy group-containing monomer is added to a portion of the carboxyl groups of the polymer to obtain an alkali-soluble resin.

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

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

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

Other monomers include N-substituted maleimides, alkyleneoxy group-containing monomers, phosphoric acid ester group-containing ethylenically unsaturated monomers, carboxyl group-containing monomers, and the like.
N-substituted maleimides include, for example, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane 1,6-bismaleimidehexane, 3-maleimidopropionic acid, 6,7-methylenedioxy- 4-methyl-3-maleimidocoumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylene dimaleimide, N, N'-1,4-phenylene dimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitro phenyl)maleimide, N-benzylmaleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, Examples include N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine, and the like.
Examples of the alkyleneoxy group-containing monomer include EO-modified cresol acrylate, n-nonylphenoxy polyethylene glycol acrylate, phenoxyethyl acrylate, ethoxylated phenyl acrylate, ethylene oxide (EO)-modified (meth)acrylate of phenol, and paracumylphenol. Examples include EO or propylene oxide (PO) modified (meth)acrylate, nonylphenol EO modified (meth)acrylate, nonylphenol PO modified (meth)acrylate, and the like.

As the carboxyl group-containing monomer, the monomers already described can be used.

The phosphoric acid ester group-containing ethylenically unsaturated monomer is, for example, a compound obtained by reacting a phosphoric acid esterifying agent such as phosphorus pentoxide or polyphosphoric acid with the hydroxyl group of the above-mentioned hydroxyl group-containing ethylenically unsaturated monomer. be.

The acid value of the alkali-soluble resin is preferably 30 to 200 mgKOH/g, more preferably 50 to 180 mgKOH/g, and even more preferably 70 to 170 mgKOH/g to impart solubility in alkali development. It is soluble in alkaline development if it has a moderate acid value. and high adhesion to the substrate.

<Alkali-soluble resin without ethylenically unsaturated groups>
The coloring composition of the present specification can contain an alkali-soluble resin having no ethylenically unsaturated group in order to adjust the degree of curing of the coating.

The weight average molecular weight (Mw) of the binder resin (C) is preferably 2,000 to 40,000, more preferably 3,000 to 300,00, and even more preferably 4,000 to 20,000. Moreover, the value of Mw/Mn is preferably 10 or less. Having a suitable mass average molecular weight (Mw) improves adhesion to the substrate and suppresses development residue.

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

The content of the binder resin (C) is preferably 20 to 400 parts by weight, more preferably 50 to 250 parts by weight, based on 100 parts by weight of the colorant (A). When contained in an appropriate amount, a film can be easily formed and good color properties can be easily obtained.

<Thermosetting compound>
The photosensitive coloring composition can contain a thermosetting compound. As a result, when producing a color filter, the heat resistance is improved because the crosslinking density is improved in the heating step after forming a pattern on the film by photolithography. Furthermore, since the pigment is less likely to aggregate during the heating process, the contrast ratio is further improved.

The thermosetting compound is a low-molecular compound or a polymer (thermosetting resin), and is not limited by molecular weight. Examples of thermosetting compounds 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.

<Photopolymerizable compound (D)>
The photosensitive coloring composition of the present invention contains a photopolymerizable compound (D). Photopolymerizable compounds include monomers or oligomers that can be cured by ultraviolet rays, heat, etc. to produce transparent resins. It is preferable that the photopolymerizable compound (D) contains a urethane-based polyfunctional monomer.

<Urethane-based polyfunctional monomer>
The urethane-based polyfunctional monomer is a monomer having a urethane bond and a plurality of polymerizable unsaturated groups. Urethane-based polyfunctional monomers can suppress curing shrinkage during photocuring due to highly flexible urethane bonds, thereby suppressing pixel defects. Improves sexual performance.

Urethane-based polyfunctional monomers include, for example, polyfunctional urethane (meth)acrylate obtained by reacting a hydroxyl group-containing (meth)acrylate with a polyfunctional isocyanate, and polyfunctional urethane (meth)acrylate obtained by reacting a polyfunctional isocyanate with alcohol, and a hydroxyl group-containing (meth)acrylate obtained by reacting a polyfunctional isocyanate with an alcohol. Examples include polyfunctional urethane acrylates obtained by reacting acrylates, and polyfunctional urethane monomers containing carboxyl groups.

Examples of hydroxyl group-containing (meth)acrylates include 2-hydroxyethyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol tri(meth)acrylate, and ditrimethylolpropane tri(meth)acrylate. meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol ethylene oxide modified penta(meth)acrylate, dipentaerythritol propylene oxide modified penta(meth)acrylate, dipentaerythritol caprolactone modified penta(meth)acrylate, glycerol acrylate Examples include 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 isocyanate include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

The urethane-based polyfunctional monomer is preferably a carboxyl group-containing urethane-based polyfunctional monomer represented by the following general formula (1). This improves developability and provides pixels with better shapes.
General formula (1)
(H ₂ C=C(R ¹ )COO) _m -X-(OCOCH(R ¹ )CH ₂ S(R ² )COOH) _n
In the general formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 12 carbon atoms, and X is an organic group having a urethane bond with a valence of (m+n) and having 3 to 60 carbon atoms. , m is an integer of 2 to 18, and n is an integer of 1 to 3.

The monomer represented by general formula (1) is obtained, for example, by reacting the polyfunctional isocyanate compound with a hydroxyl group-containing (meth)acrylate to obtain a compound having a urethane bond. Next, it can be synthesized by adding a mercapto compound having a carboxyl group as described below to the obtained compound.

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

The photopolymerizable compound (D) can contain other monomers in addition to the urethane-based polyfunctional monomer.

Other monomers include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, 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, phenoxy Tetraethylene 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 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, methylol Various acrylic esters and methacrylic esters such as (meth)acrylic acid ester of melamine, epoxy (meth)acrylate, urethane acrylate, (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, penta Examples include erythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, acrylonitrile, etc. Photopolymerizable compounds having an acid group are also preferably used, for example, polyhydric alcohols and Examples include esterification products of free hydroxyl group-containing poly(meth)acrylates with (meth)acrylic acid and dicarboxylic acids; esterification products of polyhydric carboxylic acids and monohydroxyalkyl (meth)acrylates. Specific examples include monohydroxyoligoacrylates or monohydroxyoligomethacrylates such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate. , free carboxyl group-containing monoesters with dicarboxylic acids such as malonic acid, succinic acid, glutaric acid, and phthalic acid; propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4- Tricarboxylic acids such as tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, benzene-1,3,5-tricarboxylic acid, and 2-hydroxyethyl acrylate, 2-hydroxy Examples include free carboxyl group-containing oligoesters with monohydroxy monoacrylates or monohydroxy monomethacrylates such as ethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate. Among these, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, ethylene oxide-modified trimethylolpropane tri(meth)acrylate, and propylene oxide-modified trimethylolpropane tri(meth)acrylate. ) Various acrylic esters and methacrylic esters such as acrylate are preferred.

Other monomers preferably have 3 to 12 ethylenically unsaturated groups in order to improve the sensitivity of the photosensitive coloring composition.

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

The blending amount of the photopolymerizable compound is preferably 1 to 50% by weight, more preferably 2 to 40% by weight based on 100% by weight of the nonvolatile content of the photosensitive coloring composition. When blended in an appropriate amount, curability and developability are further improved.

<Photopolymerization initiator (E)>
The photopolymerization initiator (E) is an oxime ester photopolymerization initiator [E1] whose maximum absorption peak wavelength on the longest wavelength side is less than 340 nm, and an oxime ester photopolymerization initiator [E1] whose maximum absorption peak wavelength on the longest wavelength side is 340 nm or more. Contains an ester photopolymerization initiator [E2]. When an oxime ester compound absorbs ultraviolet light, the N—O bond of the oxime is cleaved to generate iminyl radicals and alkyloxy radicals. Since these radicals generate highly active radicals by further decomposition, a pattern can be formed with a small amount of exposure. The photosensitive coloring composition contains two types of photopolymerization initiators with different wavelength ranges in which the photosensitivity is highest, so that a wide range of wavelengths from the light source can be used for photocuring, resulting in a good pattern shape, and Pixels with good adhesion to the substrate can be formed.

Oxime ester compounds are described in, for example, JP 2007-210991, JP 2009-179619, JP 2010-037223, JP 2010-215575, JP 2011-020998, etc. Examples include oxime ester photopolymerization initiators.

<Oxime ester photopolymerization initiator [E1]>
Examples of the oxime ester photopolymerization initiator [E1] include compounds represented by the following general formulas (5) to (7).

In general formulas (5) and (6), R ¹ and R ⁴ to R ⁶ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, and a linear or branched alkyl group having 3 to 20 carbon atoms. represents a cyclic alkyl group or a phenyl group. The alkyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, and a phenyl group. R ² is a linear or branched alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group, and R ³ is a linear or branched alkyl group having 1 to 12 carbon atoms. Or a branched alkyl group.

In the general formulas (5) and (6), the linear or branched alkyl group having 1 to 12 carbon atoms in R ¹ to R ⁶ is, for example, a methyl group, an ethyl group, an n-propyl group, an i -Propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-octyl group, n-nonyl group, n -decyl group, n-undecyl group, n-dodecyl group, etc. Examples of the cyclic alkyl group having 3 to 20 carbon atoms include cycloalkyl groups such as cyclopropyl group, cyclobutyl group, cyclopentyl group, cyclohexyl group, cycloheptyl group, cyclooctyl group, and cyclooctadecyl group.

Further, as substituents that can be bonded to each alkyl group and each phenyl group of R ¹ , R ⁴ to R ⁶ , alkoxyl groups include, for example, methoxy group, ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group. group, t-butoxy group, and the like. Examples of the halogen atom include a fluorine atom and a chlorine atom. Each alkyl group and each phenyl group may be substituted with two or more substituents.

In general formula (5) and general formula (6), R ¹ is preferably a methyl group, ethyl group, phenyl group, etc. from the viewpoint of synthesis and properties as a coloring composition. R ⁴ to R ⁶ are preferably hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, i-propyl groups, etc. from the viewpoint of synthesis and properties as a coloring composition.

The compound represented by the general formula (5) is, for example, 1-[4-(phenylthio)phenyl]-octan-1-one-2-one oxime-O-acetate, 1-[4-(2-methylphenylthio)phenyl ]-octan-1-one-2-one oxime-O-acetate, 1-[4-(2,4,6-trimethylphenylthio)phenyl]-octan-1-one-2-one oxime-O-acetate, 1 -[4-(2-ethylphenylthio)phenyl]-octan-1-one-2-one oxime-O-acetate, 1-[4-(phenylthio)phenyl]-octan-1-one-2-one oxime-O -benzoate, 1-[4-(2-methylphenylthio)phenyl]-octan-1-one-2-one oxime-O-benzoate, 1-[4-(2,4,6-trimethylphenylthio)phenyl] -Octane-1-one-2-one oxime-O-benzoate, 1-[4-(2-ethylphenylthio)phenyl]-octan-1-one-2-one oxime-O-benzoate and the following formula (5-1 ) can be mentioned.

Chemical formula (5-1)

The compound represented by general formula (6) is, for example, 1-[9-ethyl-6-benzoyl-9. H. -carbazol-3-yl]-octan-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9. H. -carbazol-3-yl]-ethane-1-one oxime-O-acetate, 1-[9-ethyl-6-(2-methylbenzoyl)-9. H. -carbazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-ethyl-6-(2,4,6-trimethylbenzoyl)-9. H. -carbazol-3-yl]-ethane-1-one oxime-O-benzoate, 1-[9-n-butyl-6-(2-ethylbenzoyl)-9. H. -carbazol-3-yl]-ethane-1-one oxime-O-benzoate and a compound represented by the following chemical formula (6-1).

In general formula (7), R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted Alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or It represents an unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. Note that the hydrogen atoms of the substituents in R ₁ to R ₄ may be further substituted with other substituents.

Examples of the other substituents include halogen groups such as fluorine atom, chlorine atom, bromine atom, and iodine atom; alkoxy groups such as methoxy group, ethoxy group, and tert-butoxy group; and aryl groups such as phenoxy group and p-tolyloxy group. Oxy group, methoxycarbonyl group, butoxycarbonyl group, alkoxycarbonyl group such as phenoxycarbonyl group, acyloxy group such as acetoxy group, propionyloxy group, benzoyloxy group, acetyl group, benzoyl group, isobutyryl group, acryloyl group, methacryloyl group, Acyl groups such as methoxalyl groups, alkylsulfanyl groups such as methylsulfanyl groups and tert-butylsulfanyl groups, arylsulfanyl groups such as phenylsulfanyl groups and p-tolylsulfanyl groups, alkylamino groups such as methylamino groups and cyclohexylamino groups, dialkylamino groups such as dimethylamino group, diethylamino group, morpholino group, and piperidino group; arylamino groups such as phenylamino group and p-tolylamino group; alkyl groups such as methyl group, ethyl group, tert-butyl group, and dodecyl group; In addition to aryl groups such as phenyl group, p-tolyl group, xylyl group, cumenyl group, naphthyl group, anthryl group, phenanthryl group, and benzofuranyl group, heterocyclic groups such as furyl group and thienyl group, hydroxy group, carboxy group, formyl group, mercapto group, sulfo group, mesyl group, p-toluenesulfonyl group, amino group, nitro group, cyano group, trifluoromethyl group, trichloromethyl group, trimethylsilyl group, phosphinico group, phosphono group, trimethylammoniumyl group, Examples include dimethylsulfoniumyl group and triphenylphenacylphosphoniumyl group.

Among the compounds represented by the general formula (7), compounds represented by the following chemical formulas (7-1) to (7-3) can be mentioned.

<Oxime ester photopolymerization initiator [E2]>
Examples of the oxime ester photopolymerization initiator [E2] include compounds represented by the following general formula (8) and compounds represented by the general formula (9).

General formula (8)

In general formula (8), X ¹ , X ³ and X ⁶ each independently represent R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN, and X ² has a substituent. an optionally substituted alkyl group with 1 to 20 carbon atoms; an optionally substituted aryl group with 6 to 30 carbon atoms; an optionally substituted aryl group with 7 to 3 carbon atoms; 30 arylalkyl groups or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent, and X ⁴ and X ⁵ are each independently R ¹¹ , OR ¹¹ , SR ¹¹ , COR ¹¹ , CONR ¹² R ¹³ , NR ¹² COR ¹¹ , OCOR ¹¹ , COOR ¹¹ , SCOR ¹¹ , COSR ¹¹ , COSR ¹¹ , CSOR ¹¹ , CN, a halogen atom or a hydroxyl group. R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, and a carbon atom number having 1 to 20 which may have a substituent. Represents an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms which may have a substituent, or a heterocyclic group having 2 to 20 carbon atoms which may have a substituent . a and b are each independently an integer of 0 to 3.

From the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when included in a photosensitive coloring composition, X ¹ is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Alkyl groups having 10 or less carbon atoms such as isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group, 2-ethylhexyl group; 10 carbon atoms such as cyclopentyl group, cyclohexyl group Cyclic alkyl group that may have the following side chains; 10 carbon atoms such as methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2-(1-methoxypropyl) group, 2-(1-ethoxypropyl) group, etc. An alkyl group having one ether bond in the methylene chain is preferable.

From the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when included in a photosensitive coloring composition, X ³ is hydrogen, or a methyl group, ethyl group, n-propyl group, isopropyl group, n- Alkyl groups with 6 or less carbon atoms such as butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group; 6 or less carbon atoms such as cyclopentyl group, cyclohexyl group Cyclic alkyl group: 6 or less carbon atoms such as methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2-(1-methoxypropyl) group, 2-(1-ethoxypropyl) group and has an ether bond in the methylene chain. Preferably, the alkyl group has one alkyl group.

From the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when included in a photosensitive coloring composition, X ⁶ is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Alkyl groups having 6 or less carbon atoms such as isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group; cyclic alkyl groups having 6 or less carbon atoms such as cyclopentyl group, cyclohexyl group ; Methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2-(1-methoxypropyl) group, 2-(1-ethoxypropyl) group, etc. having 6 or less carbon atoms and having one ether bond in the methylene chain Alkyl groups are preferred.

From the viewpoint of ease of synthesis, sensitivity, solubility, and storage stability when included in a photosensitive coloring composition, X ² is a methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, Alkyl groups having 6 or less carbon atoms such as isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group, cyclic alkyl groups having 6 or less carbon atoms such as cyclopentyl group, cyclohexyl group , methoxymethyl group, ethoxymethyl group, ethoxyethyl group, 2-(1-methoxypropyl) group, 2-(1-ethoxypropyl) group, etc. having 6 or less carbon atoms and having one ether bond in the methylene chain Alkyl groups are preferred.

From the viewpoint of ease ^of synthesis, sensitivity, solubility, and storage stability when included in a photosensitive coloring composition, X ⁴ and , n-butyl group, isobutyl group, t-butyl group, n-amyl group, isoamyl group, t-amyl group, n-hexyl group and the like are preferred.

Examples of the heterocyclic group having 2 to 20 carbon atoms include 3 to 7-membered heterocycles. For example, preferably pyridyl, pyrimidyl, furyl, thienyl, tetrahydrofuryl, dioxolanyl, benzoxazol-2-yl, tetrahydropyranyl, pyrrolidyl, imidazolidyl, pyrazolidyl, thiazolidyl, isothiazolidyl, oxazolidyl, isoxazolidyl, piperidyl, piperazyl, Examples include 5- to 7-membered heterocycles such as morpholinyl.

The compound represented by general formula (8) is preferably the following compound.

In general formula (9), R ₁ is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryl group, Oxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted acyl group, substituted or unsubstituted acyloxy group, substituted or unsubstituted amino group, Represents a substituted or unsubstituted phosphinoyl group, a substituted or unsubstituted carbamoyl group, or a substituted or unsubstituted sulfamoyl group.

_R2 is a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or unsubstituted aryloxy group, a substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group , represents a substituted or unsubstituted alkylsulfonyl group, a substituted or unsubstituted arylsulfonyl group, a substituted or unsubstituted acyloxy group, or a substituted or unsubstituted amino group.

R ₃ to R ₅ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or Unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group group, substituted or unsubstituted acyl group, or substituted or unsubstituted amino group.
R ₆ to R ₉ each independently represent a hydrogen atom, a halogen atom, a cyano group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, a substituted or unsubstituted aryl group, a substituted or Unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkylsulfanyl group, substituted or unsubstituted arylsulfanyl group group, substituted or unsubstituted alkylsulfinyl group, substituted or unsubstituted arylsulfinyl group, substituted or unsubstituted alkylsulfonyl group, substituted or unsubstituted arylsulfonyl group, substituted or unsubstituted amino group, or the following general formula Represents the substituent represented by (10).

一般式（１０）中、Ｒ_１’およびＲ_２’は、Ｒ_１およびＲ₂と同義である。 Ｒ₁₀～Ｒ₁₄は、それぞれ独立に、水素原子、ハロゲン原子、シアノ基、ニトロ基、ハロアルキル基、置換または未置換のアルキルスルフィニル基、置換または未置換のアリールスルフィニル基、置換または未置換のアルキルスルホニル基、置換または未置換のアリールスルホニル基、または置換または未置換のアシル基を表し、Ｒ₁₀～Ｒ₁₄の少なくとも一つは、ニトロ基、または下記一般式（１１）で示す置換基である。 General formula (10)

In general formula (10), R _1' and R _2' have the same meanings as R ₁ and R ₂ . R ₁₀ to R ₁₄ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkylsulfinyl group, a substituted or unsubstituted arylsulfinyl group, or a substituted or unsubstituted alkyl group. Represents a sulfonyl group, a substituted or unsubstituted arylsulfonyl group, or a substituted or unsubstituted acyl group, and at least one of R ₁₀ to R ₁₄ is a nitro group or a substituent represented by the following general formula (11) .

General formula (11)

In general formula (11), R ₁₅ to R ₁₉ are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, a haloalkyl group, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkyloxy group, Substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclicoxy group, substituted or unsubstituted alkenyl group, substituted or unsubstituted alkyl group Represents a sulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group.

<Other photopolymerization initiators>
Other photopolymerization initiators other than those mentioned above include, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1 -one, 1-hydroxycyclohexyl phenylketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-(dimethylamino)-1-[4-(4- morpholino)phenyl]-2-(phenylmethyl)-1-butanone, or 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1 -Acetophenone compounds such as butanone; Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, or benzyl dimethyl ketal; benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone , acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or benzophenone compounds such as 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, Thioxanthone compounds such as 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis( trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s -triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4 , 6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl) )-6-triazine, or triazine compounds such as 2,4-trichloromethyl-(4'-methoxystyryl)-6-triazine; bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide, or diphenyl-2 , 4,6-trimethylbenzoylphosphine oxide; quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, ethyl anthraquinone; borate compounds; carbazole compounds; imidazole compounds; or titanocene Examples include type compounds.

The content of the photopolymerization initiator (E) is preferably 2 to 50 parts by weight, more preferably 2 to 30 parts by weight, based on 100 parts by weight of the colorant. When incorporated in an appropriate amount, photocurability and developability are further improved.

<Sensitizer>
The photosensitive coloring composition can contain a sensitizer.
Examples of sensitizers include chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, and anthraquinones. derivatives, polymethine dyes such as 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, tetraquinoxalyloporphyrazine 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, acylphosphine 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 these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred. For example, 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 etc.

The sensitizers can be used alone or in combination of two or more.

The content of the sensitizer is preferably 3 to 60 parts by weight, more preferably 5 to 50 parts by weight, based on 100 parts by weight of the photopolymerization initiator (E). When contained in an appropriate amount, curability and developability are further improved.

<Thiol-based chain transfer agent>
The photosensitive coloring composition can contain a chain transfer agent. The chain transfer agent is preferably a thiol chain transfer agent. When a thiol-based chain transfer agent is used in combination with a photopolymerization initiator, thiyl radicals, which are less susceptible to polymerization inhibition by oxygen, are generated during radical polymerization after light irradiation, thereby improving the sensitivity of the photosensitive coloring composition.

The thiol-based chain transfer agent is preferably a certain polyfunctional thiol having two or more thiol groups (SH groups). In addition, it is more preferable that the thiol-based chain transfer agent has 4 or more SH groups. 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, tris trimercaptopropionate (2-Hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine Preferable examples include ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, and pentaerythritol tetrakisthiopropionate.

Thiol-based chain transfer agents can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 0.3 to 10% by weight, more preferably 0.3 to 8% by weight based on 100% by weight of nonvolatile content of the photosensitive coloring composition. When contained in an appropriate amount, photosensitivity and tapered shape are improved, and wrinkles are less likely to occur on the coating surface.

<Polymerization inhibitor>
The photosensitive coloring composition can contain a polymerization inhibitor. This makes it possible to suppress exposure due to diffracted light from the mask during exposure using photolithography, making it easier to obtain a pattern with a desired shape.

Examples of the polymerization inhibitor include catechol, resorcinol, 1,4-hydroquinone, 2-methylcatechol, 3-methylcatechol, 4-methylcatechol, 2-ethylcatechol, 3-ethylcatechol, 4-ethylcatechol, 2-propyl Catechol, 3-propylcatechol, 4-propylcatechol, 2-n-butylcatechol, 3-n-butylcatechol, 4-n-butylcatechol, 2-tert-butylcatechol, 3-tert-butylcatechol, 4-tert - Alkylcatechol compounds such as butylcatechol, 3,5-di-tert-butylcatechol, 2-methylresorcinol, 4-methylresorcinol, 2-ethylresorcinol, 4-ethylresorcinol, 2-propylresorcinol, 4-propylresorcinol , 2-n-butylresorcinol, 4-n-butylresorcinol, 2-tert-butylresorcinol, 4-tert-butylresorcinol and other alkylresorcinol compounds, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2 , 5-di-tert-butylhydroquinone and other alkylhydroquinone compounds, tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine and other phosphine compounds, trioctylphosphine oxide, triphenylphosphine oxide, etc. Examples include phosphine oxide compounds, phosphite compounds such as triphenyl phosphite and trisnonylphenyl phosphite, pyrogallol, and phloroglucin. Among these, alkylhydroquinone compounds such as methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, and 2,5-di-tert-butylhydroquinone are preferred.

The content of the polymerization inhibitor is preferably 0.01 to 0.8% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. In this range, the effect of the polymerization inhibitor becomes large, and the linearity of the taper, the wrinkles of the coating film, the pattern resolution, etc. become good.

<Ultraviolet absorber>
The photosensitive coloring composition can contain an ultraviolet absorber. Examples of the ultraviolet absorber include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylic acid ester compounds, cyanoacrylate compounds, and salicylate 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-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2'- Hydroxy-5'-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1 -dimethylethyl)-4-hydroxy, 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-benzotriazol-2-yl)-5-t-butyl-4-hydroxyphenyl)propionate/polyethylene glycol 300 reaction product, 2-(2H-benzotriazol-2-yl)-4-(1 , 1,3,3-tetramethylbutyl)phenol, 2,2'-methylenebis[6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)phenol] , 2-(2H-benzotriazol-2-yl)-p-cresol, 2-(5-chloro-2H-benzotriazol-2-yl)-6-t-butyl-4-methylphenol, 2-(3 , 5-di-t-amyl-2-hydroxyphenyl)benzotriazole, 2-[2-hydroxy-5-[2-(methacryloyloxy)ethyl]phenyl]-2H-benzotriazole, octyl-3-[3- tert-butyl-4-hydroxy-5-(5-chloro-2H-benzotriazol-2-yl)phenyl]propionate, 2-ethylhexyl-3-[3-tert-butyl-4-hydroxy-5-(5- Chloro-2H-benzotriazol-2-yl)phenyl]propionate is mentioned.

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

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- Octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octade Examples include siloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, and 2-hydroxy-4-methoxy-2'-carboxybenzophenone.

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

The content of the ultraviolet absorber is preferably 5 to 70% by weight based on the total of 100% by weight of the photopolymerization initiator and the ultraviolet absorber. When contained in an appropriate amount, the resolution after development is further improved.

Further, the total content of the photopolymerization initiator and the ultraviolet absorber is preferably 1 to 20% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. When contained in an appropriate amount, the adhesion between the substrate and the coating is further improved, and good resolution can be obtained.

<Antioxidant>
The photosensitive coloring composition can contain an antioxidant. Antioxidants are photopolymerization initiators and thermosetting compounds contained in photosensitive coloring compositions that can prevent yellowing due to oxidation during heat curing or the thermal process during ITO annealing, and can suppress a decrease in the transmittance of the film. . In particular, when the colorant concentration of the photosensitive coloring composition is high, the content of the photopolymerizable compound (D) decreases relatively, so if you increase the amount of photopolymerization initiator or mix the thermosetting compound, the coating tends to yellow. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process and suppress a decrease in transmittance of the film.

Examples of antioxidants include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, and hydroxylamine-based compounds. In this specification, the antioxidant is preferably a compound that does not contain a halogen atom. Among these, hindered phenol antioxidants, hindered amine antioxidants, phosphorus antioxidants, and sulfur antioxidants are preferred from the viewpoint of achieving both transmittance and sensitivity of the coating film.

Antioxidants can be used alone or in combination of two or more.

The content of the antioxidant is preferably 0.5 to 5.0% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. This further improves transmittance, spectral characteristics, and sensitivity.

<Leveling agent>
The photosensitive coloring composition can contain a leveling agent. This further improves the wettability to the transparent substrate during coating formation and the drying properties of the coating. Examples of the leveling agent include silicone surfactants, fluorine surfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

Leveling agents can be used alone or in combination of two or more.

The content of the leveling agent 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 the coating properties, pattern adhesion, and transmittance of the photosensitive coloring composition will be further improved.

<Storage stabilizer>
The photosensitive coloring composition can contain storage stabilizers. This can stabilize the viscosity of the composition over time. Storage stabilizers 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, and organic acids such as t-butylpyrocatechol, tetraethylphosphine, and tetraphenylphosphine. Examples include phosphine and phosphites.

The content of the storage stabilizer is preferably 0.1 to 10 parts by weight per 100 parts by weight of the colorant.

<Adhesion improver>
The photosensitive coloring composition can contain an adhesion improver. This further improves the adhesion between the coating and the base material. Further, it becomes easier to form a narrow pattern using photolithography. Examples of the adhesion improver include silane coupling agents.

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

The content of the adhesion improver is preferably 0.01 to 10 parts by weight, more preferably 0.05 to 5 parts by weight, per 100 parts by weight of the colorant. When contained in an appropriate amount, the photosensitivity of the photosensitive coloring composition is improved, the adhesion of the film is further improved, and the resolution of the pattern is also further improved.

<Method for producing photosensitive coloring composition>
The photosensitive coloring composition is subjected to a dispersion treatment using, for example, a colorant (A), a dispersant (B), etc. to prepare a pigment dispersion. Next, the pigment dispersion, the binder resin (C), the photopolymerizable compound (D), and the photopolymerizable initiator (E) can be mixed to produce the composition. When using two or more types of colorants (A), they can be mixed at the same time. Alternatively, pigment dispersions can be prepared separately and mixed. In addition, it is preferable to use a dispersion aid when producing a pigment dispersion.

For the dispersion treatment, a dispersion device such as a kneader, two-roll mill, three-roll mill, ball mill, horizontal sand mill, vertical sand mill, annular bead mill, or attritor can be used.

The photosensitive coloring composition can be prepared as a solvent-developable coloring composition or an alkali-developable coloring composition. The composition of these may be changed as appropriate depending on the type of developer.

<Solvent>
The photosensitive coloring composition can contain a solvent. This makes it easier to adjust the viscosity of the photosensitive coloring composition, making it easier to form a film with a smooth surface. The solvent may be appropriately selected depending on the purpose of use and may be contained in an appropriate amount.

Examples of the solvent include ester solvents (solvents containing -COO- in the molecule but not containing -O-), ether solvents (solvents containing -O- but not -COO- in the molecule), and ether ester solvents. (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- but not -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule and -O -, -CO- and -COO--free), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

The solvent is preferably an organic solvent having a boiling point of 120° C. or more and 180° C. or less at 1 atm from the viewpoint of coating properties and drying properties. The solvent is propylene glycol monomethyl ether acetate, ethyl lactate, butyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2 -Pentanone, N,N-dimethylformamide, N-methylpyrrolidone and the like are preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are more preferred.

<Removal of coarse particles>
The photosensitive coloring composition is processed into coarse particles of 5 μm or more, preferably 1 μm or more, more preferably 0.5 μm, by centrifugation at a gravitational acceleration of 3000 to 25000 G, filtration with a sintered filter or membrane filter, or the like. It is preferable to remove the above coarse particles and mixed dust. As described above, it is preferable that the photosensitive coloring composition does not substantially contain particles of 0.5 μm or more. More preferably, it is 0.3 μm or less.

<Color filter>
The color filter herein includes a base material (also referred to as a substrate or transparent substrate) and a filter segment formed from a photosensitive coloring composition. The color filter segment (hereinafter also referred to as filter segment) preferably has a red filter segment, a green filter segment, and a blue filter segment by appropriately selecting the type of coloring agent used. Moreover, the color filter can have a magenta color filter segment, a cyan color filter segment, and a yellow filter segment instead of the color filter segments. Note that a reflective substrate can be used instead of the transparent substrate. Examples of the transparent substrate include a glass substrate. Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface.

<Production method of color filter>
It is preferable to form a color filter by first forming a black matrix on a base material, and then forming filter segments. Note that the black matrix can be formed after forming a thin film transistor (TFT) on the base material in advance.
Examples of the black matrix include chromium, a multilayer film of chromium/chromium oxide, an inorganic film such as titanium nitride, and a resin film in which a light shielding agent is dispersed.

The filter segments can be formed by, for example, a printing method, an electrodeposition method, a transfer method, an inkjet method, a photolithography method, or the like. Among these methods, the photolithography method is preferred because it allows the production of highly accurate color filters.
In the photolithography method, for example, a photosensitive coloring composition containing a coloring agent of a certain color is applied onto a transparent substrate to form a film with a dry film thickness of about 0.2 to 5 μm. The obtained film (hereinafter referred to as the first film) is exposed (light irradiated) through a mask having a predetermined pattern. Next, the film is developed by immersing it in a solvent or alkaline developer or by spraying a developer, and the uncured portions are removed to obtain a desired pattern. By similarly performing this step using photosensitive coloring compositions having colorants of other colors, color filters having filter segments of each color can be manufactured. Furthermore, a second film (oxygen barrier film) can be formed on the first film before exposure using polyvinyl alcohol or a water-soluble acrylic resin. As a result, the first film does not come into contact with oxygen, so that the exposure sensitivity is further improved. Additionally, the color filter can be heated to cure uncured photopolymerizable compounds in the filter segments.

Examples of the coating device include spray coating, spin coating, slit coating, and roll coating. A drying process can be performed during coating. Examples of the drying device include a hot air oven and an infrared heater.

Examples of the alkaline developer include inorganic alkalis such as sodium carbonate and sodium hydroxide; and organic alkalis such as dimethylbenzylamine and triethanolamine. Further, an antifoaming agent and a surfactant can be added to the developer.

In this specification, the color filter can be used in applications other than liquid crystal display devices, such as solid-state image sensors, organic EL display devices, quantum dot display devices, electronic paper, and head-mounted displays.

<Liquid crystal display device>
The liquid crystal display device of this specification includes a color filter.
In the liquid crystal display device, the color filter is bonded to a counter substrate using a sealant after the filter segments are formed, liquid crystal is injected through an injection port provided in the sealing part, and then the injection port is sealed. Furthermore, a liquid crystal display device can be manufactured by bonding a polarizing film or a retardation film to the outside of the substrate as necessary.

The liquid crystal display device of the present invention includes the color filter of the present invention and a light source. Examples of the light source include a cold cathode fluorescent lamp (CCFL) and a white LED, but in the present invention, it is preferable to use a white LED because the red reproduction area is expanded. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 equipped with a color filter of the present invention. The device 10 shown in FIG. 1 includes a pair of transparent substrates 11 and 21 that are spaced apart and facing each other, and a liquid crystal LC is sealed between them.

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

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

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

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

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

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

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

The present invention will be explained below based on manufacturing examples and examples. It goes without saying that the present invention is not limited to these. In addition, "part" is "part by mass", and "%" is "% by mass". Note that Examples 64 and 65 are reference examples.

The method for measuring physical property values will be explained below.
(Average molecular weight of resin)
The number average molecular weight (Mn) and mass average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. Equipment: Using HLC-8220GPC (manufactured by Tosoh Corporation), two separation columns were connected in series, and the packing material for both was "TSK-GEL SUPER HZM-N" connected in two series, and the oven temperature was 40℃. The measurement was performed at a flow rate of 0.35 ml/min using a tetrahydrofuran (THF) solution as an eluent. The sample was dissolved in a solvent consisting of 1 wt % of the above eluent, and 20 microliters of the sample was injected. All molecular weights are polystyrene equivalent values.

(acid value of resin)
Add 80 ml of acetone and 10 ml of water to 0.5 to 1 g of the resin solution, stir to dissolve uniformly, and use a 0.1 mol/L KOH aqueous solution as the titrant using an automatic titrator ("COM-555" Hiranuma Sangyo Co., Ltd.). The acid value (mgKOH/g) of the resin solution was measured. 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.

(Ammonium salt value (mgKOH/g))
The ammonium salt value is a value calculated by titration with a 0.1N silver nitrate aqueous solution using a 5% potassium chromate aqueous solution as an indicator, and then converted to the equivalent amount of potassium hydroxide, and indicates the ammonium salt value of non-volatile components.

<Refining of diketopyrrolopyrrole red pigment>
The diketopyrrolopyrrole-based red pigment shown in Table 1, which was produced according to the example of JP-A-2017-138417, was refined as follows to obtain finely divided diketopyrrolopyrrole pigments (A1-1) to (A1-8). A pyrrole red pigment was obtained.

(Finely divided diketopyrrolopyrrole red pigment (A1-1))
100 parts of diketopyrrolopyrrole red pigment (a1-1), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 60° C. for 10 hours. Next, the kneaded mixture was poured into warm water, heated to about 80°C and stirred for 1 hour to form a slurry, filtered and washed with water to remove salt and diethylene glycol, dried at 80°C overnight, and pulverized. As a result, 96.9 parts of a finely divided diketopyrrolopyrrole red pigment (A1-1) was obtained.

(Finely divided diketopyrrolopyrrole red pigment (A1-2) to (A1 to 8)
The micronization was carried out in the same manner as the micronized diketopyrrolopyrrole-based red pigment (A1-1), except that the diketopyrrolopyrrole-based red pigment (a1-1) was changed to the pigment shown in Table 1. Ketopyrrolopyrrole red pigments (A1-2) to (A1-8) were obtained.

(Finely divided diketopyrrolopyrrole red pigment (A1-9))
The diketopyrrolopyrrole red pigment (a1-1) was mixed with C.I. I. Pigment Red 254 (“Irgafore Red B-CF”, manufactured by BASF Japan) was used, but the process was refined in the same manner as the micronized diketopyrrolopyrrole red pigment (A1-1), and the micronized diketopyrrolopyrrole A red pigment (A1-9) was obtained.

<Refining of azo pigment>
The azo pigments shown in Table 2 prepared according to the examples of Japanese Patent No. 6368844 were refined as follows to obtain (A2-1) to (A2-23).

(Production of finely divided azo pigment A2-1)
80 parts of azo pigment a2-1, 800 parts of sodium chloride, and 90 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho Co., Ltd.), kneaded at 60° C. for 6 hours, and subjected to salt milling. The obtained kneaded product was poured into 3 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight. , 78 parts of finely divided pigment (A2-1) were obtained.

(Manufacture of micronized azo pigments A2-2 to A2-23) Micronization of azo pigments Except for changing to azo pigments (a2-2) to (a2 to 23) shown in Table 2 instead of azo pigment a2-1. Finely divided pigments (A2-2) to (A2-23) were obtained in the same manner as in the production of finely divided pigment (A2-1).

(Manufacture of finely divided pigment A3-1)
Anthraquinone red pigment C. I. 500 parts of Pigment Red 177 ("Sinilex Red SR3C" manufactured by Shinic Co., Ltd.), 500 parts of sodium chloride, and 250 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded at 120°C for 8 hours. did. Next, this kneaded material was poured into 5 liters of warm water, heated to 70°C and stirred for 1 hour to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight. A finely divided organic pigment (A3-1) was obtained.

(Manufacture of finely divided pigment A3-2)
C. I. 100 parts of Pigment Red 269 (PR269) ("Toner Magenta F8B" manufactured by Clariant), 800 parts of sodium chloride, and 180 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70°C for 5 hours. . This mixture was poured into 4000 parts of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry. After repeated filtration and water washing to remove the salt and solvent, the mixture was heated to about 80°C for 24 hours. It was dried to obtain a finely divided organic pigment (A3-2).

(Manufacture of finely divided pigment A3-3)
C. I. 100 parts of Pigment Red 242 ("Novopalm Scarlet 4RF" manufactured by Clariant), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 10 hours. Next, this mixture was poured into 3 liters of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, and after repeated filtration and water washing to remove sodium chloride and solvent, It was dried at ℃ for one day and night to obtain a finely divided pigment (A3-3).

(Manufacture of finely divided pigment A4-1)
C. I. 100 parts of Pigment Yellow 138 (PY138) (“Paliotol Yellow K0960-HD” manufactured by BASF Japan), 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 heated at 80°C. The mixture was kneaded for 6 hours. This mixture was poured into 2000 parts of warm water and stirred for 1 hour while heating to 80°C to form a slurry. After repeated filtration and water washing to remove salt and solvent, it was dried at 80°C overnight to form a fine yellow pigment. (A4-1) was obtained.

<Production of finely divided pigments (A4-2) to (A4-4)>
The following quinophthalone compounds (a) to (c) were prepared according to the examples of JP-A-2012-226110.

(Manufacture of finely divided pigment (A4-2))
100 parts of quinophthalone compound (a), 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.), kneaded at 60° C. for 6 hours, and subjected to salt milling. The obtained kneaded product was poured into 3 liters of warm water and stirred for 1 hour while heating to 70°C to form a slurry. After repeated filtration and water washing to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight. , 98 parts of finely divided pigment (A4-2) were obtained.

(Manufacture of finely divided pigment (A4-3))
100 parts of quinophthalone compound (b), 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 60° C. for 8 hours. Next, this kneaded material was poured into warm water, heated to about 70°C and stirred for 1 hour to form a slurry, and after repeated filtration and water washing to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight. 98 parts of finely divided pigment (A4-3) were obtained.

(Manufacture of finely divided pigment (A4-4))
100 parts of quinophthalone compound (c), 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 60° C. for 8 hours. Next, this kneaded material was poured into warm water, heated to about 70°C and stirred for 1 hour to form a slurry, and after repeated filtration and water washing to remove sodium chloride and diethylene glycol, it was dried at 80°C overnight. 97 parts of finely divided pigment (A4-4) were obtained.

(Manufacture of finely divided pigment A4-5)
Isoindoline yellow pigment C. I. 100 parts of pigment yellow 139 ("Irgafore Yellow 2R-CF" manufactured by BASF Japan), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were placed in a 1-gallon stainless steel kneader and kneaded at 60° C. for 10 hours. Next, this mixture was poured into 3 liters of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, and after repeated filtration and water washing to remove sodium chloride and solvent, It was dried at ℃ for one day and night to obtain a finely divided organic pigment (A4-5).

(Finely divided organic pigment (A4-6))
100 parts of a metal complex yellow pigment (C.I. pigment yellow 150, "Yellow Pigment E4GN" manufactured by Lanxess Corporation), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.). The mixture was kneaded at 60°C for 10 hours. Next, this mixture was poured into 3 liters of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, and after repeated filtration and water washing to remove sodium chloride and solvent, It was dried at ℃ for one day and night to obtain a finely divided organic pigment (A4-6).

(Finely divided organic pigment (A4-7))
Yellow pigment C. I. Pigment Yellow 185 ("Paliotol Yellow D1155" manufactured by Ciba Japan): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a 1-gallon stainless steel kneader and kneaded at 120° C. for 8 hours. Next, this kneaded material was poured into 5 liters of warm water, heated to 70°C and stirred for 1 hour to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C overnight. A finely divided organic pigment (A4-7) was obtained.

(dye 1)
30 parts (calculated as non-volatile content) of Resin 1 having a cationic group in the side chain were added to 2000 parts of water, thoroughly stirred and mixed, and then heated to 60°C. Meanwhile, 10 parts of C.I. I. An aqueous solution in which Acid Red 52 was dissolved was prepared and added dropwise little by little to the resin solution. After the dropwise addition, the mixture was stirred at 60° C. for 120 minutes to fully react. To confirm the end point of the reaction, the reaction solution was dropped onto a filter paper, and the end point was determined to be the end point when there was no bleeding, and it was determined that a salt-forming compound had been obtained. After cooling to room temperature while stirring, suction filtration was performed, and after washing with water, the salt-forming compound remaining on the filter paper was dried by removing moisture in a dryer. I. A coloring agent (dye 1) which is a salt-forming compound of Acid Red 52 and Resin 1 having a cationic group in its side chain was obtained. At this time, C.I. in the colorant (dye 1) I. The content of the effective pigment component derived from Acid Red 52 was 25% by mass.

(Dye 2)
C. I. Acid Red 52 C. I. The process was carried out in the same manner as the production of the colorant (dye 1) except that Acid Red 289 was used. I. A colorant (dye 2) which is a salt-forming compound of Acid Red 289 and resin 1 having a cationic group in its side chain was obtained. At this time, C.I. in the colorant (dye 2) I. The content of the effective pigment component derived from Acid Red 289 was 27% by mass.

(Dye 3)
C. in a 1 L stainless steel reaction vessel equipped with a reflux tube under a nitrogen atmosphere. I. 5.0 parts of Basic Violet 10 (BV10: Rodamine B manufactured by Taoka Chemical Co., Ltd.) and 1.6 parts of hydroxyethyl methacrylate (HEMA) were dissolved in 40 ml of dichloromethane, and 1-(3-dimethylaminopropyl)-3-ethyl 2.2 parts of carbodiimide hydrochloride and 0.25 parts of dimethylaminopyridine were added and stirred at room temperature for 24 hours. The obtained dichloromethane solution was washed with water, dried under reduced pressure, and then purified using a silica gel column to obtain a colorant (dye 3).

(Manufacture of dye solution a-1)
The following mixture was stirred and mixed so as to be uniform, and then filtered through a filter with a pore size of 5.0 μm to prepare a colored composition (dye solution a-1).
Coloring agent (dye 1) 20.0 parts Propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc)
50.0 parts Solvent (S) 30.0 parts The solvent (S) is a mixed solvent (S) containing parts by mass of each of the following (S-1) to (S-4).
(S-1) PGMAc 30 parts (S-2) 3-methoxybutanol 20 parts (S-3) Ethyl 3-ethoxypropionate 20 parts (S-4) n-Butyl acetate 20 parts

(Manufacture of dye solutions a-2 and 3)
In the same manner as dye solution a-1, dye solutions a-2 and a-3 were prepared using colorants (dye 2 and dye 3), respectively.

<Dye derivative>
The following dye derivatives (hereinafter also referred to as derivatives) were used.

(Manufacture of resin type dispersant solution (B-1))
In a reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer, 6 parts of 3-mercapto-1,2-propanediol, 9.7 parts of pyromellitic dianhydride, 23.5 parts of cyclohexanone, 0.01 part of mono-n-butyltin(IV) oxide was added to each, and the atmosphere was replaced with nitrogen gas. The inside of the reaction vessel was heated to 100° C. and reacted for 7 hours. After confirming that 97% or more of the acid anhydride was half-esterified by measuring the acid value, the temperature in the system was cooled to 70°C, 80 parts of methyl methacrylate and 20 parts of hydroxyethyl methacrylate were charged, and 2. A solution of 0.1 part of 2'-azobisisobutyronitrile dissolved in 26.2 parts of cyclohexanone was added and reacted for 10 hours. It was confirmed by non-volatile content measurement that 95% of the polymerization had progressed, and the reaction was terminated. After the reaction was completed, the nonvolatile content was adjusted to 40% with PGMAc to obtain a resin-type dispersant solution (B-1) having an acid value of 43 mgKOH/g and a mass average molecular weight of 9,500.

(Manufacture of resin type dispersant solution (B-2))
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 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 completed, and PGMAc was added to dilute the non-volatile content to 40%, and the acid value was 70 mgKOH/g, mass average. A resin-type dispersant solution (B-2) having a molecular weight of 8,500 was obtained.

(Manufacture of resin type dispersant solution (B-3))
62.6 parts of 1-dodecanol, 287.4 parts of ε-caprolactone, and 0.1 part of monobutyltin(IV) oxide as a catalyst were charged into a reaction vessel equipped with a gas inlet tube, a thermometer, a condenser, and a stirrer, and nitrogen gas was added. After replacing the mixture with , it was heated and stirred at 120° C. for 4 hours. After confirming that 98% of the reaction had occurred by measuring non-volatile content, 73.3 parts of pyromellitic anhydride was added, and the mixture was reacted at 120° C. for 2 hours. After measuring the acid value, it was confirmed that 98% or more of the acid anhydride had been half-esterified, and the reaction was terminated. A resin type dispersant solution (B-3) with a nonvolatile content of 40% was obtained by adjusting the nonvolatile content with PGMAc. The obtained dispersant was a white solid at room temperature, had an acid value of 49 mgKOH/g, and a mass average molecular weight of 5,000.

<Example of manufacturing binder resin (C) liquid>
<Production of binder resin (C1: non-photosensitive resin)>
(Preparation of binder resin (C1-1) liquid)
196 parts of PGMAc was charged into a reaction vessel equipped with a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas introduction tube, a dropping tube, and a stirring device, the temperature was raised to 80°C, and the inside of the reaction vessel was replaced with nitrogen. From, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), A mixture of 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition was completed, the reaction was continued for an additional 3 hours to obtain an acrylic resin solution. After cooling to room temperature, 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 PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20%. A binder resin (C1-1) solution was prepared. The mass average molecular weight (Mw) was 26,000.

(Preparation of binder resin (C1-2) liquid)
A nitrogen atmosphere was placed in a flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel, and a nitrogen introduction tube, and 210 parts of PGMAc was added thereto, and the temperature was raised to 100° C. with stirring. Next, 106 parts of benzyl methacrylate, 22 parts of acrylic acid, and 22 parts of dicyclopentanyl methacrylate (FA-513M, manufactured by Hitachi Chemical Co., Ltd.) were dissolved in 215 parts of PGMAc, and further 3.6 parts of 2,2'-azobisisobutyronitrile was dissolved. A solution of the acrylic resin was added dropwise into a flask and stirred at 100° C. for 5 hours to obtain a solution of the acrylic resin. 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 PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20%. A binder resin was prepared, and a resin (C1-2) solution having a mass average molecular weight (Mw) of 10,000 was obtained.

(Preparation of binder resin (C1-M) liquid)
A binder resin (C1-M) liquid was prepared by mixing and stirring equal amounts of a binder resin (C1-1) liquid and a binder resin (C1-2) liquid.

<Production example of binder resin (C2: photosensitive resin)>
(Preparation of binder resin (C2-1) liquid)
207 parts of PGMAc 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, and the inside of the reaction vessel was replaced with nitrogen. From, 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 PGMAc was added dropwise at 70° C. over 3 hours. After the dropwise addition was completed, the reaction was continued for an additional hour to obtain an acrylic resin solution. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content, and PGMAc was added to the previously synthesized resin solution so that the nonvolatile content was 20%. A binder resin (C2-1) was prepared. The mass average molecular weight (Mw) was 18,000.

(Preparation of binder resin (C2-2) liquid)
333 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), 71.1 parts (0.50 mol) of glycidyl methacrylate, 22.0 parts (0.10 mol) of tricyclodecane skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and A solution prepared by adding 3.6 parts of azobisisobutyronitrile to a mixture of 164 parts of PGMAc was added dropwise into the flask from the dropping funnel over 2 hours, and the mixture was further stirred at 100° C. for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 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 photosensitive transparent resin solution with an acid value of 80 mgKOH/g. . After cooling to room temperature, about 2 parts of the photosensitive transparent resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. A binder resin (C2-2) liquid was prepared by adding PGMAc so that the binder resin (C2-2) liquid was obtained. The mass average molecular weight (Mw) was 12,000.

(Adjustment of binder resin (C2-3) liquid)
182 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% of benzyl methacrylate was added. 5 parts (0.40 mol), 43.0 parts (0.5 mol) of methacrylic acid, 22.0 parts (0.10 mol) of tricyclodecane skeleton monomethacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.), and PGMAc136 A solution prepared by adding 3.6 parts of azobisisobutyronitrile to a mixture consisting of 1.5 parts and 3.6 parts of azobisisobutyronitrile was added dropwise into the flask from the dropping funnel over 2 hours, and the mixture was further stirred at 100°C for 5 hours. Next, the atmosphere inside the flask was changed from nitrogen to air, and 35.5 parts of glycidyl methacrylate [0.25 mol, (50 mol % based on the carboxyl group of methacrylic acid used in this reaction)] and 0 parts of trisdimethylaminomethylphenol were added. .9 parts and 0.145 parts of hydroquinone were put into the flask, and the reaction was continued at 110° C. for 6 hours to obtain a photosensitive transparent resin solution with an acid value of 79 mgKOH/g. After cooling to room temperature, about 2 parts of the photosensitive transparent resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content. A binder resin (C2-3) solution was prepared by adding PGMAc so that the binder resin (C2-3) solution was obtained. The mass average molecular weight (Mw) was 13,000.

(Preparation of binder resin (C2-4) liquid)
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, A well-stirred mixture of 120 parts of methyl methacrylate, 4 parts of t-butylperoxy-2-ethylhexanoate ("Perbutyl O" manufactured by NOF Corporation), and 40 parts of PGMAc was prepared, and used as a chain transfer agent dropping tank. A mixture of 8 parts of n-dodecanethiol and 32 parts of PGMAc was prepared by stirring thoroughly.
After charging 395 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 of the reaction tank was raised to 110°C. 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 in the same manner to obtain a binder resin (C2-4) liquid. The mass average molecular weight (Mw) of the resin was 18,000, and the acid value per nonvolatile content was 2 mgKOH/g.

(Preparation of binder resin (C2-M) liquid)
A binder resin (B2-M) solution was prepared by mixing and stirring equal amounts of four types of binder resin (C2-1) to (C2-4) solutions.

<Production method of colored composition (single color)>
[Manufacture example 1]
(Preparation of colored composition (R-1))
The following mixture was stirred and mixed until it was homogeneous, and then 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. The mixture was filtered through a 0 μm filter to produce a colored composition (R-1) containing 20.0% by mass of non-volatile components.
Pigment (A1-1): 14.0 parts Resin type dispersant solution (B-1 non-volatile content 40%): 3.0 parts Binder resin solution (C1-M: non-volatile content 20%): 24.0 parts Solvent ( S): 59.0 copies

[Production Examples 2 to 47]
(Preparation of colored compositions (R-2) to (R-47))
Colored compositions (R-2) to (R-47) were produced in the same manner as in Production Example 1, except that the material types and masses were changed as listed in Table 3.

<Production method of colored composition (coloring material mixture)>
[Manufacture example 101]
(Preparation of colored composition (X-1))
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a colored composition (X-1).
Coloring composition solution (R-1: 20% non-volatile content): 78.0 parts Binder resin solution (C1-M: 20% non-volatile content): 8.0 parts Solvent (S): 14.0 parts

[Production Examples 102 to 152]
(Preparation of colored compositions (X-2 to 52))
Colored compositions (X-2 to X-52) were produced in the same manner as Production Example 101, except that the material types and masses were changed as listed in Table 4.

<Method for producing photosensitive coloring composition>
[Example 1]
(Photosensitive coloring composition (Y-1))
The following raw materials were mixed, stirred, and filtered through a filter with a pore size of 1.0 μm to obtain a photosensitive coloring composition (Y-1).
Coloring composition (X-1: nonvolatile content 17.2%): 50.0 parts Binder resin solution (C2-M: nonvolatile content 20%): 15.0 parts Thermosetting compound (BE-1): 1. 0 parts Thermosetting compound (BE-2): 1.0 parts Photopolymerizable monomer (D1-1): 3.0 parts Photopolymerization initiator (E1-1): 1.2 parts Photopolymerization initiator (E2-1): 0.69 part Sensitizer (F): 0.2 part Thiol chain transfer agent (G): 0.4 part Polymerization inhibitor (H-1): 0.01 part Ultraviolet absorber (I): 0.1 part Antioxidant (J): 0.1 part Leveling agent (K: 3% non-volatile content): 1.0 part Storage stabilizer (L): 0.1 part Silane coupling agent ( M): 0.2 parts Solvent (S): 26.0 parts

[Examples 2 to 78, Comparative Examples 1 to 4]
(Preparation of photosensitive coloring composition (Y-2 to 82))
Photosensitive coloring compositions (Y-2 to Y-82) were prepared in the same manner as in Example 1, except that the material type and mass were changed as shown in Table 5. Note that Examples 53, 55, and 63 in this specification are reference examples.

<Thermosetting compound (BE)>
・Epoxy compound (BE-1)
(BE-1-1) 1,2- of 2,2'-bis(hydroxymethyl)-1-butanol
Epoxy-4-(2-oxiranyl)cyclohexane adduct
[EHPE-3150 (manufactured by Daicel)],
(BE-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase ChemteX)],
(BE-1-3) Triglycidyl isocyanurate (BE-1-1) to (BE-1-3) were mixed in equal amounts to prepare an epoxy compound (BE-1).

・Oxetane compound (BE-2):
3-Ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane
[Aron oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)]

<Photopolymerizable compound (D)>
(D1-1) Prepared by the following method.
In a four-necked flask, 210 parts of dipentaerythritol pentaacrylate, 34 parts of hexamethylene diisocyanate, and 0.5 parts of N,N-dimethylbenzylamine were charged, and the mixture was reacted at a temperature of 50 to 70°C for 8 hours. - Disappearance of isocyanate absorption in ^{No. 1} was confirmed. Next, 21 parts of mercaptopropionic acid and 0.6 parts of 4-methoxyphenol were charged, and the reaction was carried out at a temperature of 50 to 60°C for 6 hours to form a carboxyl group represented by the following chemical formula (12), which is a urethane-based polyfunctional monomer. A containing polyfunctional monomer (D1-1) was obtained.

Chemical formula (12)

(D1-2) Prepared by the following method.
In a four-necked flask, 582 parts of dipentaerythritol hexaacrylate/pentaacrylate mixture, 36 parts of hexamethylene diisocyanate, and 0.5 part of N,N-dimethylbenzylamine were charged and reacted at a temperature of 50 to 70°C for 8 hours. A photopolymerizable compound (D1-2) which is a urethane-based polyfunctional monomer was obtained.

(D1-3) Prepared by the following method.
In a four-necked flask, 432 parts of pentaerythritol triacrylate and 84 parts of hexamethylene diisocyanate were charged and reacted at 60°C for 8 hours to form a mixture containing a photopolymerizable compound (D1-3) which is a urethane-based polyfunctional monomer. The product was obtained.

(D1-4) A mixture of the hexaacrylate/pentaacrylate mixture of dipentaerythritol and the photopolymerizable compound (D1-1) in the same amount.
(D2) The following "D2-1 to 5" were mixed in the same amount to prepare a photopolymerizable compound (D2).
"D2-1" Trimethylolpropane triacrylate
[Aronix M309 (manufactured by Toagosei Co., Ltd.)]
"D2-2" dipentaerythritol penta and hexaacrylate
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]
"D2-3" polybasic acidic acrylic oligomer
[Aronix M520 (manufactured by Toagosei Co., Ltd.)]
"D2-4" Caprolactone modified dipentaerythritol hexaacrylate
[KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]
"D2-5" bifunctional bisphenol A type (meth)acrylate
[ABE-300 (manufactured by Shin Nakamura Chemical Co., Ltd.)]
"D2-6" Ethoxylated isocyanuric acid triacrylate
[A-9300 (manufactured by Shin Nakamura Chemical Co., Ltd.)]

<Photopolymerization initiator (E1-1)>
1-[4-(phenylthio)phenyl]-octan-1-one-2-one oxime-O-benzoate [Irgacure OXE01 (manufactured by BASF Japan)]
<Photopolymerization initiator (E1-2)>
1-[9-ethyl-6-(2-methylbenzoyl)-9. H. -Carbazol-3-yl]-ethane-1-one oxime-O-acetate [Irgacure OXE02 (manufactured by BASF Japan)]
<Photopolymerization initiator (E1-3)>
Compound represented by chemical formula (5-1) <Photopolymerization initiator (E1-4)>
Compound represented by chemical formula (6-1) <Photopolymerization initiator E2-1 to E2-4>
The above photopolymerization initiators E2-1 to E2-4 were synthesized by the following method.

<Synthesis of photopolymerization initiator (E2-1)>
(Step 1)
In a nitrogen stream, 12.60 parts (95 mmol) of aluminum chloride, 126 parts of 1,2-dichloroethane, and 53 mmol of N-ethyl-3-nitro-carbazole were charged into an ice-cooled reaction vessel. While maintaining the reaction temperature below 5° C., 64 mmol of 4-(2-methoxy-1-methyl-ethoxy)-2-methyl-benzoyl chloride was gradually added dropwise to this mixture. After the dropwise addition was completed, the mixture was stirred at 20° C. for 4 hours. Thereafter, the reaction solution was poured into ice water to separate it into an oily phase and an aqueous phase, and the liquid constituting this oily phase was dried using magnesium sulfate. Next, the desiccant was removed from this liquid by filtration, and the solvent was further removed by distillation. As described above, an acyl body was obtained.

(Step 2)
In a nitrogen stream, 20 mmol of the above acyl compound, 2.1 parts (30 mmol) of hydroxylamine hydrochloride, and 16.9 parts of dimethylformamide were charged into a reaction vessel. This mixture was stirred at 80° C. for 1 hour, then cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent was removed from the liquid constituting the oily phase by distillation, and then 25.4 parts of butyl acetate and 2.45 parts (24 mmol) of acetic anhydride were added to the distillation residue. This mixed solution was stirred at 90° C. for 1 hour, then cooled to room temperature and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil-water separation, the solvent was removed by distillation from the liquid constituting the oily phase, and further recrystallization was performed using ethyl acetate as a solvent. In the manner described above, a photopolymerization initiator (E2-1) was obtained.

<Synthesis of photopolymerization initiator (E2-2)>
(Step 1)
In a nitrogen stream, 12.60 parts (95 mmol) of aluminum chloride, 126 parts of 1,2-dichloroethane, and 53 mmol of N-(2-ethyl-hexyl)-3-nitrocarbazole compound were placed in an ice-cooled reaction vessel. I invested in it. While maintaining the reaction temperature below 5° C., 64 mmol of 4-(2-methoxy-1-methyl-ethoxy)-2-methyl-benzoyl chloride was gradually added dropwise to this mixture. After the dropwise addition was completed, the mixture was stirred at 20° C. for 4 hours. Thereafter, the reaction solution was poured into ice water to separate it into an oily phase and an aqueous phase, and the liquid constituting this oily phase was dried using magnesium sulfate. The desiccant was removed from this liquid by filtration, and the solvent was further removed by distillation. As described above, an acyl body was obtained.

(Step 2)
In a nitrogen stream, 20 mmol of the above acyl compound, 2.1 parts (30 mmol) of hydroxylamine hydrochloride, and 16.9 parts of dimethylformamide were charged into a reaction vessel. This mixture was stirred at 80° C. for 1 hour, then cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent was removed from the liquid constituting the oily phase by distillation, and then 25.4 parts of butyl acetate and 2.45 parts (24 mmol) of acetic anhydride were added to the distillation residue. This mixed solution was stirred at 90° C. for 1 hour, then cooled to room temperature and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil-water separation, the solvent was removed by distillation from the liquid constituting the oily phase, and further recrystallization was performed using ethyl acetate as a solvent. In the manner described above, a photopolymerization initiator (E2-2) was obtained.

<Synthesis of photopolymerization initiator (E2-3)>
(Step 1)
In a nitrogen stream, 12.60 parts (95 mmol) of aluminum chloride, 126 parts of 1,2-dichloroethane, and 53 mmol of an N-ethyl-3-nitrocarbazole compound were charged into an ice-cooled reaction vessel. While maintaining the reaction temperature below 5° C., 64 mmol of 4-(ethoxymethyl)-2-methyl-benzoyl chloride was gradually added dropwise to this mixture. After the dropwise addition was completed, the mixture was stirred at 20° C. for 4 hours. Thereafter, the reaction solution was poured into ice water to separate it into an oily phase and an aqueous phase, and the liquid constituting this oily phase was dried using magnesium sulfate. The desiccant was removed from this liquid by filtration, and the solvent was further removed by distillation. As described above, an acyl body was obtained.

(Step 2)
In a nitrogen stream, 20 mmol of the above acyl compound, 2.1 parts (30 mmol) of hydroxylamine hydrochloride, and 16.9 parts of dimethylformamide were charged into a reaction vessel. This mixture was stirred at 80° C. for 1 hour, then cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent was removed from the liquid constituting the oily phase by distillation, and then 25.4 parts of butyl acetate and 2.45 parts (24 mmol) of acetic anhydride were added to the distillation residue. This mixed solution was stirred at 90° C. for 1 hour, then cooled to room temperature and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil-water separation, the solvent was removed by distillation from the liquid constituting the oily phase, and further recrystallization was performed using ethyl acetate as a solvent. In the manner described above, a photopolymerization initiator (E2-3) was obtained.

<Synthesis of photopolymerization initiator (E2-4)>
(Step 1)
In a nitrogen stream, 12.60 parts (95 mmol) of aluminum chloride, 126 parts of 1,2-dichloroethane, and 53 mmol of N-(2-ethyl-hexyl)-3-nitrocarbazole compound were placed in an ice-cooled reaction vessel. I invested in it. While maintaining the reaction temperature below 5° C., 64 mmol of 4-(2-methoxy-1-methyl-ethoxy)-2-methyl-benzoyl chloride was gradually added dropwise to this mixture. After the dropwise addition was completed, the mixture was stirred at 20° C. for 4 hours. Thereafter, the reaction solution was poured into ice water to separate it into an oily phase and an aqueous phase, and the liquid constituting this oily phase was dried using magnesium sulfate. The desiccant was removed from this liquid by filtration, and the solvent was further removed by distillation. As described above, an acyl body was obtained.
(Step 2)
In a nitrogen stream, 20 mmol of the above acyl compound, 2.1 parts (30 mmol) of hydroxylamine hydrochloride, and 16.9 parts of dimethylformamide were charged into a reaction vessel. This mixture was stirred at 80° C. for 1 hour, then cooled to room temperature and separated into an oily phase and an aqueous phase. The solvent was removed from the liquid constituting the oily phase by distillation, and then 25.4 parts of butyl acetate and 3.12 parts (24 mmol) of propionic anhydride were added to the distillation residue. This mixed solution was stirred at 90° C. for 1 hour, then cooled to room temperature and neutralized with a 5% aqueous sodium hydroxide solution. Subsequently, this was subjected to oil-water separation, the solvent was removed by distillation from the liquid constituting the oily phase, and further recrystallization was performed using ethyl acetate as a solvent. In the manner described above, a photopolymerization initiator (E2-4) was obtained.

<Photopolymerization initiator E2-5 to E2-8>
[Synthesis of photopolymerization initiator (E2-5)]
100.0 parts of N-benzophenoylcarbazole was dissolved in 1000 ml of chloroform, 85.0 parts of aluminum chloride was added, and while stirring at 0°C, a solution of 32.0 parts of propionyl chloride dissolved in 500 ml of chloroform was mixed with 2 It dripped over time. After the dropwise addition was completed, the mixture was stirred at 25° C. for 4 hours. The reaction solution was poured into 2000 parts of ice water and extracted with 2000 mL of chloroform. After drying the organic layer over magnesium sulfate and filtering off the desiccant, the residue was recrystallized from chloroform/methanol to obtain 113.0 parts of intermediate compound (a1). Next, to a solution of 100.0 parts of compound (a1), 1000 ml of tetrahydrofuran, and 500 ml of concentrated hydrochloric acid, 38.4 parts of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature. After the dropwise addition was completed, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml x 3 times), dried over magnesium sulfate, the desiccant was filtered, the solvent was distilled off, and the residue was washed with n-hexane to obtain precursor compound (b1) 99 .8 copies were obtained. Next, 30.0 parts of compound (b1) was stirred in 300 ml of ethyl acetate, 6.3 parts of acetic anhydride and 10.6 parts of sodium acetate were added, and the mixture was heated under reflux for 3 hours. After that, the reaction solution was poured into 500 ml of ice water, the constituent organisms were extracted with ethyl acetate, the organic layer was washed with water (300 ml x 3 times), and after drying with magnesium sulfate, the desiccant was filtered and the solvent was distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 31.4 parts of photopolymerization initiator (E2-5).

Photopolymerization initiator (E2-5)

[Synthesis of photopolymerization initiator (E2-6)]
100.0 parts of N-benzophenoylcarbazole was dissolved in 1000 ml of chloroform, 84.0 parts of aluminum chloride was added, and while stirring at 0°C, a solution of 36.8 parts of butanoyl chloride dissolved in 500 ml of chloroform was added. The mixture was added dropwise over 2 hours. After the dropwise addition was completed, the mixture was stirred at 25° C. for 4 hours. The reaction solution was poured into 2000 parts of ice water and extracted with 2000 mL of chloroform. After drying the organic layer over magnesium sulfate and filtering off the desiccant, the residue was recrystallized from chloroform/methanol to obtain 109.3 parts of intermediate compound (a2). Next, to a solution of 100.0 parts of compound (a2), 1000 ml of tetrahydrofuran, and 500 ml of concentrated hydrochloric acid, 43.1 parts of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature. After the dropwise addition was completed, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml x 3 times), dried over magnesium sulfate, the desiccant was filtered, the solvent was distilled off, and the residue was washed with n-hexane to obtain precursor compound (b2) 89 .I got 3 copies. Next, 30.0 parts of compound (b2) was stirred in 300 ml of ethyl acetate, 6.1 parts of acetic anhydride and 10.3 parts of sodium acetate were added, and the mixture was heated under reflux for 3 hours. After that, the reaction solution was poured into 500 ml of ice water, the constituent organisms were extracted with ethyl acetate, the organic layer was washed with water (300 ml x 3 times), and after drying with magnesium sulfate, the desiccant was filtered and the solvent was distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 30.0 parts of photopolymerization initiator (E2-6).

Photopolymerization initiator (E2-6)

[Synthesis of photopolymerization initiator (E2-7)]
Dissolve 100.0 parts of N-(p-nitrophenyl)carbazole in 1000 ml of chloroform, add 101.8 parts of aluminum chloride, and dissolve 44.3 parts of butanoyl chloride in 500 ml of chloroform while stirring at 0°C. The solution was added dropwise over 2 hours. After the dropwise addition was completed, the mixture was stirred at 25° C. for 4 hours. The reaction solution was poured into 2000 parts of ice water and extracted with 2000 mL of chloroform. After drying the organic layer with magnesium sulfate and filtering off the desiccant, the residue was recrystallized with chloroform/methanol to obtain 113.6 parts of intermediate compound (a3). Next, to a solution of 100.0 parts of compound (a3), 1000 ml of tetrahydrofuran, and 500 ml of concentrated hydrochloric acid, 43.1 parts of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature. After the dropwise addition was completed, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1500 ml of chloroform. The organic layer was washed with water (500 ml x 3 times), dried over magnesium sulfate, the desiccant was filtered, the solvent was distilled off, and the residue was washed with n-hexane to obtain precursor compound (b3) 107. .I got 2 copies. Next, 50.0 parts of compound (b3) was stirred in 500 ml of ethyl acetate, 19.9 parts of acetic anhydride and 11.7 parts of sodium acetate were added, and the mixture was heated under reflux for 3 hours. After that, the reaction solution was poured into 500 ml of ice water, the constituent organisms were extracted with ethyl acetate, the organic layer was washed with water (500 ml x 3 times), and after drying with magnesium sulfate, the desiccant was filtered and the solvent was distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 57.6 parts of photopolymerization initiator (E2-7).

Photopolymerization initiator (E2-7)

[Synthesis of photopolymerization initiator (E2-8)]
100.0 parts of N-benzophenoyl-1,3-dimethyl-carbazole was dissolved in 1000 ml of chloroform, 78.6 parts of aluminum chloride was further added, and while stirring at 0°C, 29.6 parts of propionyl chloride was dissolved in chloroform. A solution dissolved in 500 ml was added dropwise over 2 hours. After the dropwise addition was completed, the mixture was stirred at 25° C. for 4 hours. The reaction solution was poured into 2000 parts of ice water and extracted with 2000 mL of chloroform. After drying the organic layer with magnesium sulfate and filtering off the desiccant, the residue was recrystallized with chloroform/methanol to obtain 111.8 parts of intermediate compound (a4). Next, to a solution of 100.0 parts of compound (a4), 1000 ml of tetrahydrofuran, and 500 ml of concentrated hydrochloric acid, 35.7 parts of tert-butyl nitrite was added dropwise over 1 hour while stirring at room temperature. After the dropwise addition was completed, the mixture was stirred at room temperature for 5 hours. The reaction solution was poured into 1600 ml of ice water and extracted with 1600 ml of chloroform. The organic layer was washed with water (500 ml x 3 times), dried over magnesium sulfate, the desiccant was filtered, the solvent was distilled off, and the residue was washed with n-hexane to obtain precursor compound (b4) 98 .I got 3 copies. Next, 30.0 parts of compound (b4) was stirred in 300 ml of ethyl acetate, 5.9 parts of acetic anhydride and 10.0 parts of sodium acetate were added, and the mixture was heated under reflux for 3 hours. After that, the reaction solution was poured into 500 ml of ice water, the constituent organisms were extracted with ethyl acetate, the organic layer was washed with water (300 ml x 3 times), and after drying with magnesium sulfate, the desiccant was filtered and the solvent was distilled off. The residue was recrystallized from ethyl acetate-hexane to obtain 31.2 parts of photopolymerization initiator (E2-8).

Photopolymerization initiator (E2-8)

<Photopolymerization initiator (E3-1, E3-2)>
(E3-1) 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone
[Irgacure 379 (manufactured by BASF Japan)]
(E3-2) 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one
[Irgacure 907 (manufactured by BASF Japan)]

<Photopolymerization initiator (E3-M)>
(E3-1) 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone
[Omnirad 379EG (manufactured by IGM Resins)]
(E3-2) 2-Methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one
[Omnirad 907 (manufactured by IGM Resins)]
(E3-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
[Omnirad TPO (manufactured by IGM Resins)]
(E3-4) 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole
[Biimidazole (manufactured by Kurogane Kasei Co., Ltd.)]
(E3-5) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine Co., Ltd.)]
(E3-6) 1-[4-(2-hydroxyethoxy)-phenyl] -2-hydroxy-2-methyl-1-propan-1-one
[Omnirad 2959 (manufactured by IGM Resins)]
(E3-7) Bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide
[Omnirad 819 (manufactured by IGM Resins)
The above (E3-1) to (E3-7) were mixed in the same amount to prepare a photopolymerization initiator (E3-M).

<Sensitizer (F)>
(F-1) 2,4-diethylthioxanthone
[Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(F-2) 4,4'-bis(diethylamino)benzophenone
[CHEMARK DEABP (manufactured by Chemark Chemical)]
As described above, (F-1) and (F-2) were mixed in the same amount to prepare a sensitizer (F).

<Thiol chain transfer agent (G)>
(G-1) Trimethylolethane tris (3-mercaptobutyrate)
[TEMB (manufactured by Showa Denko)]
(G-2) Trimethylolpropane tris (3-mercaptobutyrate)
[TPMB (manufactured by Showa Denko)]
(G-3) Pentaerythritol tetrakis (3-mercaptopropionate)
[PEMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(G-4) Trimethylolpropane tris (3-mercaptopropionate)
[TMMP (manufactured by Sakai Chemical Industry Co., Ltd.)]
(G-5) Tris[(3-mercaptopropionyloxy)-ethyl]-isocyanurate
[TEMPIC (manufactured by Sakai Chemical Industry Co., Ltd.)]
The above (G-1) to (G-5) were mixed in the same amount to prepare a thiol-based chain transfer agent (G).

<Polymerization inhibitor (H)>
(H-1) Methylhydroquinone (H-2) 3-methylcatechol (H-3) t-butylhydroquinone (HM) (H-1) to (H-3) are mixed in equal amounts, This was used as a polymerization inhibitor (HM).

<Ultraviolet absorber (I)>
(I-1) 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1 ,3,5-triazine
[TINUVIN400 (manufactured by BASF Japan)]
(I-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol
[TINUVIN900 (manufactured by BASF Japan)]
The above (I-1) to (I-2) were mixed in the same amount to prepare the ultraviolet absorber (I).

<Antioxidant (J)>
(J-1) Pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (J-2) Dioctadecyl 3,3'-thiodipropanoate (J-3) Tris[2 , 4-di-(t)-butylphenyl]phosphine (J-4) bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (J-5) p-octylphenyl salicylate or more, (J -1) to (J-5) were mixed in the same amount to prepare an antioxidant (J).

<Leveling agent (K)>
BYK-330 manufactured by BYK Chemie Co., Ltd. 1 copy,
1 copy of "Mega Fac F-551" manufactured by DIC,
A mixed solution in which 1 part of "Emulgen 103" manufactured by Kao Corporation was dissolved in 97 parts of PGMAc.

<Storage stabilizer (L)>
(L-1) 2,6-bis(1,1-dimethylethyl)-4-methylphenol (“BHT” manufactured by Honshu Chemical Industry Co., Ltd.)
(L-2) Triphenylphosphine (“TPP” manufactured by Hokuko Chemical Industry Co., Ltd.)
The above (L-1) to (L-2) were mixed in the same amount to prepare a storage stabilizer (L).

<Adhesion improver: silane coupling agent (M)>
(M-1) 3-glycidoxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-403 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-2) 3-methacryloxypropyltriethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBE-503 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-3) N-2-(aminoethyl)-3-aminopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-603 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
(M-4) 3-Mercaptopropyltrimethoxysilane
[Shin-Etsu Silicone Silane Coupling Agent KBM-803 (manufactured by Shin-Etsu Chemical Co., Ltd.)]
The above (M-1) to (M-4) were mixed in the same amount to prepare a silane coupling agent (M).

<Evaluation of photosensitive coloring composition>
Sensitivity and coating film foreign matter tests were conducted in the following manner. The test results are shown in Table 6. The evaluation criteria are as follows.
〇: Good △: Practical ×: Not suitable for practical use

The obtained photosensitive coloring composition was applied to a glass substrate measuring 10 cm long x 10 cm wide by a spin coating method, and then heated in a clean oven at 70° C. for 15 minutes to remove the solvent and obtain a coating of about 2 μm. Ta. Next, after cooling this glass substrate to room temperature, it was exposed to light at doses of 15, 20, and 50 mJ/cm using an ultra-high pressure mercury lamp through a photomask with a stripe pattern of 100 μm width (pitch 200 μm) and 25 μm width (pitch 50 μm). ^2. Substrates with different values were fabricated. Thereafter, this substrate was spray developed using a sodium carbonate aqueous solution at 23° C., washed with ion-exchanged water, air-dried, and heated in a clean oven at 230° C. for 30 minutes to produce a filter segment. Spray development was performed for the coating film of each photosensitive coloring composition for the shortest time possible to form a pattern without any remaining development, and this was defined as the appropriate development time. Note that the thickness of the coating film was measured using Dektak 3030 (manufactured by Nippon Vacuum Technology Co., Ltd.).

[Sensitivity evaluation]
The thickness of the pattern at the 100 μm photomask portion of the obtained filter segment was measured, and the minimum exposure amount that was 90% or more of the thickness immediately after coating was evaluated. The smaller the minimum exposure amount, the higher the sensitivity and the better the photosensitive coloring composition. The evaluation criteria are as follows.
○: Less than 20 mJ/cm ² △: 20 mJ/cm ² or more and less than 50 mJ/cm ² ×: 50 mJ/cm ² or more

<Pattern shape evaluation>
[Linearity evaluation]
The linearity of the pattern in the 100 μm photomask portion of the filter segment obtained by exposure to 50 mJ/cm ² ultraviolet light was observed and evaluated using an optical microscope. The evaluation criteria are as follows.
○: Good linearity △: Partially poor linearity (slight chipping)
×: Poor linearity

[Cross-sectional shape evaluation]
The cross section of the pattern in the 100 μm photomask portion of the filter segment obtained by exposure to 50 mJ/cm ² ultraviolet rays was observed and evaluated using an electron microscope. The evaluation criteria are as follows. Note that the turn cross section has a good forward taper.
〇: Smooth forward tapered cross section △: Forward tapered cross section ×: Reverse tapered cross section

<Adhesion>
The obtained photosensitive coloring composition was placed on a 100 mm x 100 mm, 0.7 mm thick glass substrate (substrate 1), and on a substrate (substrate 2) in which a silicon nitride film was formed on the surface of a TFT type liquid crystal driving substrate. The coating was applied using a spin coater at a rotation speed such that the film thickness after heating and drying was 3 μm. After drying under reduced pressure, ultraviolet light was exposed using an ultra-high pressure mercury lamp at an integrated light amount of 50 mJ/cm ² and an illumination intensity of 30 mW/cm ^{2 through a photomask containing a regular hexagonal hole with a diameter of 3} to 30 μm and a thin line of 25 μm. Thereafter, using a 0.04% by mass potassium hydroxide aqueous solution as a developer, the coating film was developed for an additional 40 seconds from the point where the unexposed portion was removed to form a pattern. Thereafter, it was dried by heating at 230° C. for 60 minutes to prepare an evaluation board.
Next, the pattern in the 25 μm photomask portion of the formed filter segment was observed and evaluated using an optical microscope. The evaluation ranks are as follows. The adhesion of this coating film was visually evaluated according to the following criteria.
○: No pattern peeling is observed.
Δ: Slight peeling of the pattern is observed.
×: Many pattern peelings are observed.

10 Liquid crystal display device 11 Transparent substrate 12 TFT array 13 Transparent electrode layer 14 Alignment layer 15 Polarizing plate 21 Transparent substrate 22 Color filter 23 Transparent electrode layer 24 Alignment layer 25 Polarizing plate 30 Backlight unit 31 White LED light source LC Liquid crystal

Claims (5)

Contains a colorant (A), a dispersant (B), a binder resin (C), a photopolymerizable compound (D), a photopolymerization initiator (E),
The colorant (A) contains a diketopyrrolopyrrole red pigment (A1),
The photopolymerizable compound (D) contains a carboxyl group-containing urethane-based polyfunctional monomer represented by the following general formula (1),
The photopolymerization initiator (E) is an oxime ester photopolymerization initiator that is a compound selected from the following general formula (5) and the following general formula (7) and has a maximum absorption peak wavelength on the longest wavelength side of less than 340 nm. [E1],
and a photosensitive coloring composition comprising an oxime ester photopolymerization initiator [E2] having a maximum absorption peak wavelength of 340 nm or more on the longest wavelength side.
General formula (1)
(H ₂ C=C(R ¹ )COO) _m -X-(OCOCH(R ¹ )CH ₂ S(R ² )COOH) _n
[In the general formula (1), R ¹ is a hydrogen atom or a methyl group, R ² is a hydrocarbon group having 1 to 12 carbon atoms, and X is an organic group having a urethane bond with a valence of (m+n) and having 3 to 60 carbon atoms; m represents an integer of 2 to 18, and n represents an integer of 1 to 3. ]


[In general formula (5), R ¹ and R ⁴ to R ⁶ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 12 carbon atoms, or a cyclic alkyl group having 3 to 20 carbon atoms. , or phenyl group. The alkyl group and phenyl group may be substituted with a substituent selected from the group consisting of a halogen atom, an alkoxyl group having 1 to 6 carbon atoms, and a phenyl group. R ² represents a linear or branched alkyl group having 1 to 12 carbon atoms, or an alkyl group having 1 to 20 carbon atoms substituted with a cycloalkyl group.
In general formula (7), R ₁ , R ₂ , R ₃ , and R ₄ each independently represent a hydrogen atom, a halogen atom, a cyano group, a nitro group, a substituted or unsubstituted alkenyl group, a substituted or unsubstituted Alkyl group, substituted or unsubstituted alkyloxy group, substituted or unsubstituted aryl group, substituted or unsubstituted aryloxy group, substituted or unsubstituted heterocyclic group, substituted or unsubstituted heterocyclic oxy group, substituted or It represents an unsubstituted alkylsulfanyl group, a substituted or unsubstituted arylsulfanyl group, a substituted or unsubstituted acyl group, or a substituted or unsubstituted amino group. Note that the hydrogen atoms of the substituents in R ₁ to R ₄ may be further substituted with other substituents. ] Furthermore, it contains a polymerization inhibitor (F),
The photosensitive coloring composition according to claim 1, which contains the polymerization inhibitor (F) in an amount of 0.01 to 0.8% by mass based on 100% by mass of the nonvolatile content of the photosensitive coloring composition. The photosensitive coloring composition according to claim 1 or 2 , further comprising one or more organic pigments (A2) selected from the group consisting of organic pigments represented by the following general formulas (2) and (3).
General formula (2)


[In general formula (2), R ₁ represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group . R ₂ and R ₃ each independently represent a hydrogen atom, an alkyl group that may have a substituent, and a phenyl group that may have a substituent.
X ₁ to X ₄ each independently represent a hydrogen atom, an alkyl group which may have a substituent, an alkoxy group which may have a substituent, a hydroxy group, a cyano group, a nitro group, a carboxyl group, a sulfo group , represents a halogen atom. ]

General formula (3)


[In general formula (3), R ₄ represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, an optionally substituted aryloxy group . R ₅ and R ₆ each independently represent a hydrogen atom, an alkyl group which may have a substituent, and a phenyl group which may have a substituent.
X ₅ to X ₁₂ each independently represent a hydrogen atom, an alkyl group that may have a substituent, an alkoxy group that may have a substituent, a hydroxy group, a cyano group, a nitro group, or a halogen atom. A represents a direct bond or a divalent linking group. The divalent linking group is an alkylene group which may have a substituent, -O-, -S-, -CO-, -SO ₂ -, -COO-, -CONH-, -SO ₂ NH- represent. ] A color filter comprising a base material and a filter segment formed from the photosensitive coloring composition according to any one of claims 1 to 3 . Claim4A liquid crystal display device comprising the color filter described above.

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