JP7334615B2 - Photosensitive coloring composition, color filter, and liquid crystal display device - Google Patents

Description

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

A color filter has a filter segment formed by patterning a film formed of a photosensitive coloring composition by a photolithography method. However, in some cases, a film that is not completely dissolved in the developer that is detached from the film contained in the developer waste discharged in the photolithography method adheres to the manufacturing equipment and contaminates it, and it is necessary to stop the manufacturing process for cleaning. There were productivity issues.

Therefore, in Patent Document 1, a coloring agent, a binder resin containing a structural unit derived from a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond, a polymerizable compound, and A photosensitive coloring composition containing a polymerization initiator is disclosed.

JP 2019-95530 A

However, conventional photosensitive coloring compositions have problems of insufficient development solubility and pattern linearity when developed at a low exposure amount of 50 mJ/m ² or less.

An object of the present invention is to provide a photosensitive coloring composition capable of forming a film having good development solubility and pattern linearity even when developed at a low exposure dose of 50 mJ/m ² or less.

The photosensitive coloring composition of the present invention contains an organic pigment (A), a dispersant (B), an alkali-soluble resin (C), a photopolymerizable compound (D), and a photopolymerization initiator (E),
The alkali-soluble resin (C) contains a polycyclic alicyclic monomer unit (c1) and an aromatic-containing monomer unit (c2) at a molar ratio of (c1)/(c2) = 5 to 0.3. The photopolymerizable compound (D) contains a carboxyl group-containing polyfunctional compound (D1).

According to the present invention, there are provided a photosensitive coloring composition, a color filter, and an image display device capable of forming a film having good development solubility and pattern linearity even when developing with a low exposure amount of 50 mJ/m ² or less. can.

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

Terms used herein are defined. "(Meth)acryloyl", "(meth)acryl", "(meth)acrylic acid", "(meth)acrylate", or "(meth)acrylamide" unless otherwise specified , “acryloyl and/or methacryloyl”, “acrylic and/or methacrylic”, “acrylic acid and/or methacrylic acid”, “acrylate and/or methacrylate”, or “acrylamide and/or methacrylamide”. References herein to "C.I." mean Color Index (C.I.). Colorants include pigments and dyes. A monomer is a polymerizable unsaturated group-containing compound. A polymerizable unsaturated group is ethylenically unsaturated groups, such as a vinyl group and a (meth)acryloyl group.

The photosensitive coloring composition of the present invention contains an organic pigment (A), a dispersant (B), an alkali-soluble resin (C), a photopolymerizable compound (D), and a photopolymerization initiator (E),
The alkali-soluble resin (C) contains a polycyclic alicyclic monomer unit (c1) and an aromatic-containing monomer unit (c2) at a molar ratio of (c1)/(c2) = 5 to 0.3. The photopolymerizable compound (D) contains a carboxyl group-containing polyfunctional compound (D1). The photosensitive coloring composition of the present invention is preferably used, for example, for producing color filters.

<Organic Pigment (A)>
A photosensitive coloring composition contains an organic pigment (A). The organic pigment is preferably a pigment having high color developability and high heat resistance, particularly a pigment having high heat decomposition resistance. Examples of organic pigments suitable for color filter applications are shown below by color index numbers.

Red pigments include, for example, C.I. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53: 3, 57, 57:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81: 3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 235, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, 277, 278, 279, 280, 281, 282, 283, 284, 285, 286, 287, 291, 295, 296, the pigment described in JP-A-2014-134712, the pigment described in Japanese Patent No. 6368844, the following general formula (4) and pigments represented by the following general formula (5).

general formula (4)

[In general formula (4), R ₁ represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted aryloxy group . R ₂ and R ₃ each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted phenyl group.
X ₁ to X ₄ are each independently 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 (5)

[In general formula (5), R ₄ represents a halogen atom, an optionally substituted alkyl group, an optionally substituted alkoxy group, or an optionally substituted aryloxy group . _R5 and _R6 each independently represent a hydrogen atom, an optionally substituted alkyl group, or an optionally substituted phenyl group.
X ₅ to X ₁₂ 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 or a halogen atom. A represents a direct bond or a divalent linking group. The divalent linking group includes an optionally substituted alkylene group, —O—, —S—, —CO—, —SO ₂ —, —COO—, —CONH—, and —SO ₂ NH—. represent. ]

Among these, C.I. I. Pigment Red 48: 1, 122, 177, 224, 242, 269, 254, 291, 295, 296, the pigment described in JP-A-2014-134712, the pigment described in Japanese Patent No. 6368844, the general formula Pigments represented by (4) and pigments represented by general formula (5) are preferred, and C.I. I. Pigment Red 177, 254, 291, 295, 296, pigments described in JP-A-2014-134712, pigments described in Japanese Patent No. 6368844, pigments represented by general formula (4), general formula (5) Pigments represented by are more preferable.

The red pigment is C.I. I. An orange pigment such as Pigment Orange 36, 38, 43, 51, 55, 59, 61, 71, or 73 and/or a yellow pigment described later may be used in combination.

Blue pigments include, 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, C.I. I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, or 15:6 is preferred, and C.I. I. Pigment Blue 15:6 is more preferred. The blue pigment may be used in combination with a purple pigment, which will be described later.

Purple pigments include, 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 and the like. Among these, C.I. I. Pigment Violet 19 or 23 is preferred, 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, and pigments described in JP-A-2017-111398. Among these, C.I. I. Pigment Green 36, 58, 59, 62, 63 and the pigments described in JP-A-2017-111398 are preferred. A yellow pigment, which will be described later, can be used in combination with the green pigment.

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. I. Pigment Yellow 138, 139, 150, 185, 231, 233, pigments described in JP-A-2012-226110 are preferred, and C.I. I. Pigment Yellow 138, 139, 150, 185, 231, 233, and pigments described in JP-A-2012-226110 are more preferable.

Cyan color pigments include, for example, C.I. I. Pigment Blue 15:1, 15:2, 15:4, 15:3, 15:6, 16, 81 and the like.

Magenta color pigments include, for example, C.I. I. Pigment Violet 1, 19, C.I. I. Pigment Red 144, 146, 177, 169, 81 and the like. A magenta color pigment can be used in combination with a yellow pigment.

In this specification, an inorganic pigment can be used in combination as a coloring agent. Inorganic pigments include, for example, titanium oxide, barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron oxide (III)), cadmium red, ultramarine blue, Prussian blue, chromium oxide green, cobalt green, amber, Synthetic iron black etc. are mentioned.

<Refinement of organic pigment (A)>
It is preferable that the organic pigment (A) is mixed with other raw materials after being subjected to a refining treatment. Refining methods include, for example, wet grinding, dry grinding, dissolution precipitation, and the like. Salt milling treatment by a kneader method, which is one type of wet grinding, is preferred herein.
The average primary particle size of the pigment is preferably 10-80 nm, more preferably 15-70 nm. If the average primary particle size is appropriate, the dispersibility is further improved, and the contrast ratio is also further improved. The average primary particle size is obtained by averaging about 20 particles from an enlarged image of a TEM (transmission electron microscope).

The salt milling treatment is a mixture of a pigment, a water-soluble inorganic salt, and a water-soluble organic solvent, for example, a kneader, two-roll mill, three-roll mill, ball mill, attritor, sand mill, planetary mixer, etc. batch type or In this treatment, the mixture is mechanically kneaded while being heated using a continuous kneader, and then washed with water to remove the water-soluble inorganic salt and the water-soluble organic solvent. The water-soluble inorganic salt functions 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 the salt milling treatment of the pigment, it is possible to obtain a pigment having a very fine primary particle size, a narrow distribution width, and a sharp particle size distribution.

Examples of water-soluble inorganic salts include sodium chloride, potassium chloride, sodium sulfate and the like. Among these, sodium chloride (table salt) is preferable from the point of price. The amount of the water-soluble inorganic salt to be used is preferably 50 to 2000 parts by mass, more preferably 300 to 1000 parts by mass, based on 100 parts by mass of the organic pigment (A), from the viewpoint of both processing 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 (miscible in) water and does not substantially dissolve water-soluble inorganic salts. The water-soluble organic solvent is preferably a high boiling point solvent having a boiling point of 120° C. or higher because it is difficult to volatilize due to the temperature rise during salt milling. Water-soluble organic solvents include, for example, 2-methoxyethanol, 2-butoxyethanol, 2-(isopentyloxy)ethanol, 2-(hexyloxy)ethanol, diethylene glycol, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol, triethylene glycol monomethyl ether, liquid polyethylene glycol, 1-methoxy-2-propanol, 1-ethoxy-2-propanol, dipropylene glycol, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, liquid polypropylene glycol, etc. mentioned. The amount of the water-soluble organic solvent used is preferably 5 to 1000 parts by mass, more preferably 50 to 500 parts by mass, based on 100 parts by mass of the organic pigment (A).

A resin can be added as needed during the salt milling process. Resins include, for example, natural resins, modified natural resins, synthetic resins, and synthetic resins modified with natural resins. The resin is preferably solid at room temperature, water-insoluble, and more preferably partially soluble in water-soluble organic solvents. The amount of the resin used is preferably 5 to 200 parts by mass with respect to 100 parts by mass of the organic pigment (A).
<Dye>
In this specification, dyes can be used in combination as colorants.
Dyes include, for example, acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfur dyes. In addition, dye derivatives and lake pigments obtained by converting dyes into lakes are also included.

In addition, the dye is a salt-forming compound of an acid dye and a quaternary ammonium salt compound, a tertiary amine compound, a secondary amine compound, or a primary amine compound; a salt-forming compound such as a resin component having an amino group and an acid dye. etc. A salt-forming compound of an acid dye and a compound having an onium base is also preferable because of its excellent fastness. The compound having an onium base is preferably a resin having a cationic group in its side chain.

Also included are salt-forming compounds of basic dyes and organic acids, perchloric acid, or metal salts thereof. Among salt-forming compounds, salt-forming compounds of basic dyes are preferable because they are excellent in various resistances and compatibility with pigments.

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.), quinoneimine 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 dyes, indigo dyes, thioindigo dyes, quinoline dyes, nitro dyes, nitroso dyes, rhodamine dyes, and the like; Among these, 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. Specific structures of dyes are described in "Handbook of Dyes" (edited by Synthetic Organic Chemistry Society; Maruzen, 1970), "Color Index" (The Society of Dyers and Colorists), and "Dye Handbook" (edited by Okawara et al.; Kodansha, 1986). etc.

<Dye derivative>
A photosensitive coloring composition can contain a dye derivative as needed. The dye derivative adsorbs to the surface of the organic pigment (A), so that the surface of the organic pigment (A) has polarity and becomes more compatible with the dispersant (B), thereby improving the dispersibility of the organic pigment (A). improves. A dye derivative is a known dye derivative having an acidic group, a basic group, a neutral group, or the like in an organic dye residue. Dye derivatives include, for example, compounds having acidic substituents such as sulfo, carboxy, or phosphate groups, and amine salts thereof, sulfonamide groups, or terminally basic substituents such as tertiary amino groups. compounds, and compounds having neutral substituents such as phenyl groups and phthalimidoalkyl groups.

Organic dyes include, for example, diketopyrrolopyrrole pigments, anthraquinone pigments, quinacridone pigments, dioxazine pigments, perinone pigments, perylene pigments, thiazineindigo pigments, triazine pigments, benzimidazolone pigments, benzoiso Indole pigments such as indole, isoindoline pigments, isoindolinone pigments, quinophthalone pigments, naphthol pigments, threne pigments, metal complex pigments, azo pigments such as azo, disazo and polyazo.

Specifically, diketopyrrolopyrrole-based dye derivatives, JP 2001-220520, WO2009/081930, WO2011/052617, WO2012/102399, JP 2017-156397, phthalocyanine Dye derivatives, JP-A-2007-226161, WO2016/163351 pamphlet, JP-A-2017-165820, Japanese Patent No. 5753266, anthraquinone-based dye derivatives, JP-A-63-264674, JP-A-09 -272812, JP-A-10-245501, JP-A-10-265697, JP-A-2007-079094, WO2009/025325, quinacridone dye derivatives, JP-A-48-54128, JP-A-03-9961, JP-A-2000-273383, dioxazine-based dye derivatives, JP-A-2011-162662, thiazineindigo-based dye derivatives, JP-A-2007-314785, triazine-based dye derivatives , JP-A-61-246261, JP-A-11-199796, JP-A-2003-165922, JP-A-2003-168208, JP-A-2004-217842, JP-A-2007-314681 , JP-A-2009-57478 for benzoisoindole-based dye derivatives, JP-A-2003-167112 for quinophthalone-based dye derivatives, JP-A-2006-291194, JP-A-2008-31281, JP-A-2012 -226110, naphthol dye derivatives, JP 2012-208329, JP 2014-5439, azo dye derivatives, JP 2001-172520, JP 2012-172092, acidic Substituents, JP-A-2004-307854, basic substituents, JP-A-2002-201377, JP-A-2003-171594, JP-A-2005-181383, JP-A-2005-213404 The dye derivatives described are mentioned. In these documents, the dye derivative may be described as a derivative, a pigment derivative, a dispersant, a pigment dispersant, or simply as a compound. A compound having a substituent such as a neutral group is synonymous with a dye derivative.

A dye derivative can be used individually or in combination of 2 or more types.

The amount of the dye derivative used is preferably 1 to 100 parts by mass, more preferably 3 to 70 parts by mass, and even more preferably 5 to 50 parts by mass, based on 100 parts by mass of the organic pigment (A).

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

<Dispersant (B)>
A known resin-type dispersant can be used as the dispersant (B). The resin-type dispersant has a colorant affinity site that adsorbs to the organic pigment (A) and a relaxation site that has a high affinity with components other than the organic pigment (A) and causes steric repulsion between dispersed particles.
Among dispersants (B), resin-type dispersants having an acidic functional group include, for example, urethane-based dispersants such as polyurethane, polycarboxylic acid esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acids (partially ) Amine 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 Oil-based dispersants such as amides and their salts formed by reaction with polyesters having carboxyl groups, (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene - Maleic acid copolymer, polyvinyl alcohol, polyvinylpyrrolidone and other water-soluble resins and water-soluble polymer compounds, polyesters, modified polyacrylates, ethylene oxide/propylene oxide addition compounds, phosphate esters, etc. .

In addition, the resin-type dispersant having a basic functional group is a nitrogen atom-containing graft copolymer or a nitrogen atom having a functional group containing a tertiary amino group, a quaternary ammonium base, a nitrogen-containing heterocyclic ring, etc. in the side chain. Containing acrylic block copolymers, urethane polymer dispersants, and the like.

The amount of the dispersant (B) used is preferably 3 to 200% by mass, more preferably 5 to 100% by mass, based on the total amount of the coloring agent. When used in an appropriate amount, the film formability is further improved.

<Alkali-soluble resin (C)>
Alkali-soluble resin (C) is a binder resin for imparting development solubility in the alkali development step during color filter production, and requires an acidic group. Also, the alkali-soluble 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 more preferably 95% or more. In terms of curability, the alkali-soluble resin (C) includes, for example, thermoplastic resins and active energy ray-curable resins. In addition, the said active-energy-ray-curable resin is hereafter called resin (C1) containing a polymerizable unsaturated group. The alkali-soluble resin (C) has, for example, acidic groups such as carboxyl groups and sulfone groups. The acidic group is preferably a carboxyl group. A carboxyl group is formed by copolymerizing a carboxyl group-containing monomer. In addition, the alkali-soluble resin (C) can have units derived from other monomers.

The alkali-soluble resin (C) contains a polycyclic alicyclic monomer unit (c1) and an aromatic-containing monomer unit (c2) at a molar ratio of (c1)/(c2) = 5 to 0.3. It is a resin that When it is included in an appropriate ratio, the developing solubility of the alkali-soluble resin (C) is greatly improved. Needless to say, the resin system of the alkali-soluble resin (C) is not limited. Incidentally, (c1)/(c2) is preferably 4 to 0.4.

Further, in all the monomer units constituting the main chain of the alkali-soluble resin (C), the aromatic-containing monomer unit (c2) preferably contains 4 to 38 mol%, preferably 10 to 38 mol%. is more preferred. This greatly improves the development solubility. The total amount of monomer units constituting the main chain is the total amount of monomers used for polymerization, and does not include monomers added to the polymer.

The polycyclic alicyclic monomer forming the polycyclic alicyclic monomer unit (c1) is, for example, tricyclo[5.2.1.0 ^2,6 ]decan-8-yl (meth)acrylate ( Common name is said to be "dicyclopentanyl (meth)acrylate".It may also be called "tricyclodecyl (meth)acrylate".), tricyclo[5.2.1.0 ^2,6 ]decene- 8-yl (meth)acrylate (commonly called "dicyclopentenyl (meth)acrylate"), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, phenyl (Meth)acrylate, cyclohexyl acrylate, 2-methylcyclohexyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate and the like.

The aromatic-containing monomer that forms the aromatic-containing monomer unit (c2) is, for example, styrene, styrenes such as α-methylstyrene, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate aromatic (Meth)acrylates having a ring; phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, phenoxytetraethyleneglycol (meth)acrylate, phenoxyhexaethyleneglycol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, parac Milphenoxyethyl (meth)acrylate, paracumylphenoxyethylene glycol (meth)acrylate, paracumylphenoxypolyethylene glycol (meth)acrylate, nonylphenoxypolyethyleneglycol (meth)acrylate, nonylphenoxypolypropylene glycol (meth)acrylate, and nonylphenoxy poly (poly)alkylene glycol (meth)acrylates having an aromatic ring such as (ethylene glycol-propylene glycol) (meth)acrylate;

Carboxyl group-containing monomers include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid. Monocarboxylic acids and the like can be mentioned.

<Resin (C1) containing a polymerizable unsaturated group>
The alkali-soluble resin (C) is preferably a resin (C1) containing a polymerizable unsaturated group. Resin (C1) containing a polymerizable unsaturated group can be synthesized, for example, by the following method (i) or (ii). By having a polymerizable unsaturated group, the resin is three-dimensionally crosslinked by light irradiation, thereby increasing the crosslink density and improving resistance to water stains and chemicals. Incidentally, the water stain is a developer-derived stain remaining on the film surface after development.

[Method (i)]
Method (i), for example, first synthesizes a polymer of an epoxy group-containing monomer, a polycyclic alicyclic monomer, an aromatic-containing monomer and other monomers. Next, a method of obtaining a resin (C1) containing a polymerizable unsaturated group by adding a monocarboxyl group-containing monomer to the epoxy group of the polymer, and reacting the resulting hydroxyl group with a polybasic acid anhydride. is. The monocarboxyl group-containing monomer is a monomer having one carboxyl group.

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)acrylates can be mentioned. Among these, glycidyl (meth)acrylate is preferred from the viewpoint of reactivity with the carboxyl group-containing monomer.

Monocarboxyl group-containing monomers include (meth)acrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, α-position haloalkyl, alkoxyl, halogen, nitro, and cyano-substituted (meth)acrylic acid. and the like.

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

Other monomers include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, isopropyl (meth) acrylate, n-butyl (meth) acrylate, isobutyl (meth) acrylate, t- Butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl (meth)acrylate, stearyl (meth)acrylate, lauryl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, isobornyl (meth)acrylate, phenyl (meth)acrylate (meth)acrylates such as acrylate, benzyl (meth)acrylate, phenoxyethyl (meth)acrylate, phenoxydiethylene glycol (meth)acrylate, methoxypolypropylene glycol (meth)acrylate, or ethoxypolyethylene glycol (meth)acrylate;
Alternatively, (meth)acrylamide, N,N-dimethyl(meth)acrylamide, N,N-diethyl(meth)acrylamide, N-isopropyl(meth)acrylamide, diacetone (meth)acrylamide, or (meth)acrylamide such as acryloylmorpholine Styrenes such as acrylamides styrene or α-methylstyrene, vinyl ethers such as ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, or isobutyl vinyl ether, fatty acid vinyls such as vinyl acetate or vinyl propionate etc.

Also, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy-4-methyl-3-maleimide coumarin, 4,4'-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N'-1,3-phenylenedimaleimide, N,N'-1,4- Phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-trichlorophenyl)maleimide, N-(4-aminophenyl)maleimide, N-(4-nitrophenyl)maleimide, N-benzyl Maleimide, N-bromomethyl-2,3-dichloromaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-3-maleimidopropionate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimide Hexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, N-substituted maleimides such as 9-maleimidoacridine, EO-modified cresol acrylate, n-nonylphenoxypolyethylene glycol acrylate, phenoxyethyl acrylate, phenyl ethoxylate Acrylates, ethylene oxide (EO)-modified (meth)acrylates of phenol, EO- or propylene oxide (PO)-modified (meth)acrylates of paracumylphenol, EO-modified (meth)acrylates of nonylphenol, PO-modified (meth)acrylates of nonylphenol, etc. is mentioned.

As a method similar to method (i), for example, a part of the carboxyl groups of a copolymer obtained by copolymerizing a monocarboxyl group-containing monomer and other monomers is added with an epoxy group-containing monomer There is also a method of synthesizing a resin (C1) containing a polymerizable unsaturated group by addition reaction.

[Method (ii)]
Method (ii) involves copolymerizing a hydroxyl group-containing monomer, a polycyclic alicyclic monomer, an aromatic-containing monomer, and other monomers to form a polymer. There is also a method of synthesizing the polymerizable unsaturated group-containing resin (C1) by reacting the hydroxyl groups of the polymer with the isocyanate groups of the isocyanate group-containing monomer.

Hydroxyl group-containing monomers, for example, 2-hydroxyethyl (meth) acrylate, 2- or 3-hydroxypropyl (meth) acrylate, 2- or 3- or 4-hydroxybutyl (meth) acrylate, glycerol mono (meth) Examples include acrylates or hydroxyalkyl methacrylates such as cyclohexanedimethanol mono(meth)acrylate. In addition, polyether mono(meth)acrylate obtained by addition polymerization of ethylene oxide, propylene oxide, and/or butylene oxide to hydroxyalkyl (meth)acrylate, poly γ-valerolactone, poly ε-caprolactone, and/or poly Polyester mono(meth)acrylates to which 12-hydroxystearic acid or the like is added are also included. 2-Hydroxyethyl methacrylate or glycerol mono(meth)acrylate is preferred from the viewpoint of suppressing foreign matter on the coating film, and from the viewpoint of sensitivity, it is preferable to use one having 2 to 6 hydroxyl groups. is preferred, and glycerol mono(meth)acrylate is more preferred.

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

Examples of the other monomers include N-substituted maleimides, alkyleneoxy group-containing monomers, phosphate ester group-containing monomers, in addition to the other monomers described in method (i).
N-substituted maleimides include, for example, cyclohexylmaleimide, phenylmaleimide, methylmaleimide, ethylmaleimide, 1,2-bismaleimidoethane, 1,6-bismaleimidohexane, 3-maleimidopropionic acid, 6,7-methylenedioxy- 4-methyl-3-maleimidocoumarin, 4,4′-bismaleimidodiphenylmethane, bis(3-ethyl-5-methyl-4-maleimidophenyl)methane, N,N′-1,3-phenylenedimaleimide, N, N'-1,4-phenylenedimaleimide, N-(1-pyrenyl)maleimide, N-(2,4,6-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, N-succinimidyl-6-maleimidohexanoate, N-[4-(2-benzimidazolyl)phenyl]maleimide, 9-maleimidoacridine and the like. Examples of alkyleneoxy group-containing monomers 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)acrylates, nonylphenol EO-modified (meth)acrylates, nonylphenol PO-modified (meth)acrylates, and the like.

Each raw material used for synthesizing the alkali-soluble resin (C) can be used alone or in combination of two or more.

The photosensitive coloring composition contains, as an alkali-soluble resin (C), a polycyclic alicyclic monomer unit (c1) and an aromatic-containing monomer unit (c2) (c1)/(c2)=5 to 0 Resins other than those contained in a .3 molar ratio can be included. The resin is, for example, an acrylic resin having an acidic group, an α-olefin/(anhydride) maleic acid copolymer, a styrene/styrenesulfonic acid copolymer, an ethylene/(meth)acrylic acid copolymer, or an isobutylene/( anhydrous) maleic acid copolymer and the like. Among these, acrylic resins and styrene/styrenesulfonic acid copolymers are preferred.

The weight average molecular weight (Mw) of the alkali-soluble resin (C) in the present invention is 2,000 or more and 40,000 or less, preferably 3,000 or more and 300,00 or less, in order to impart alkali development solubility. 4,000 or more and 20,000 or less are more preferable. Also, the value of Mw/Mn is preferably 10 or less. An appropriate weight average molecular weight improves the adhesion of the coating to the substrate and developability.

The acid value of the alkali-soluble resin (C) is preferably from 50 to 200 mgKOH/g, more preferably from 70 to 180 mgKOH/g, even more preferably from 90 to 170 mgKOH/g, in order to impart solubility in alkali development. A moderate acid value allows both developability and adhesion to be achieved at a high level. In addition, Mn is a number average molecular weight.

Alkali-soluble resin (C) can be used alone or in combination of two or more.

The content of the alkali-soluble resin (C) is preferably 20 to 400 parts by mass, more preferably 50 to 250 parts by mass, based on 100 parts by mass of the organic pigment (A). When contained in an appropriate amount, a film can be easily formed, and good color characteristics can be easily obtained.

<Thermoplastic resin>
The photosensitive coloring composition can use a thermoplastic resin that does not have alkali solubility as a binder resin.
Thermoplastic resins include, for example, acrylic resin, butyral resin, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, polyvinyl acetate, polyurethane resin, polyester resin, vinyl resin, alkyd Resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, and the like.

<Photopolymerizable compound (D)>
The photopolymerizable compound (D) includes monomers and oligomers that are cured by ultraviolet rays to form transparent resins.
The photopolymerizable compound (D) contains a carboxyl group-containing polyfunctional compound (D1). This makes it possible to achieve a high level of compatibility between photocurability and development solubility.
A carboxyl group-containing polyfunctional compound (D1) is a compound having a plurality of carboxyl groups and polymerizable unsaturated groups. The carboxyl group-containing polyfunctional compound (D1) is, for example, (1) an esterified product of a hydroxyl group-containing poly(meth)acrylate, which is a reaction product of a polyhydric alcohol and (meth)acrylic acid, and a dicarboxylic acid, and (2) Examples thereof include esters of polyvalent carboxylic acids and monohydroxyalkyl (meth)acrylates.

The number of polymerizable unsaturated groups in the carboxyl group-containing polyfunctional compound (D1) is preferably 2 to 8, more preferably 3. This makes it easy to obtain just the right amount of photocurability.

Carboxyl group-containing polyfunctional compound (D1) is, for example, succinic acid-modified trimethylolpropane diacrylate, succinic acid-modified pentaerythritol triacrylate, succinic acid-modified dipentaerythritol pentaacrylate, phthalic acid-modified trimethylolpropane diacrylate, phthalic acid Modified pentaerythritol triacrylate, phthalic acid-modified dipentaerythritol pentaacrylate, malonic acid-modified trimethylolpropane diacrylate, malonic acid-modified pentaerythritol triacrylate, malonic acid-modified dipentaerythritol pentaacrylate, malonic acid-modified trimethylolpropane triacrylate, etc. is mentioned. Among these, compounds having three polymerizable unsaturated groups are preferably succinic acid-modified pentaerythritol triacrylate, phthalic acid-modified pentaerythritol triacrylate, and malonic acid-modified pentaerythritol triacrylate.

In this specification, the mass ratio of the alkali-soluble resin (C) and the carboxyl group-containing polyfunctional compound (D1) is preferably (C)/(D1) = 0.02 to 15, more preferably 0.02 to 13. . As a result, water stains, pattern straight lines and developing solubility are further improved.

The content of the carboxyl group-containing polyfunctional compound (D1) is preferably 2 to 35% by mass, more preferably 5 to 25% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. This further improves pattern straight lines and development solubility.

In this specification, the acid value of the alkali-soluble resin (C) is preferably lower than the acid value of the carboxyl group-containing polyfunctional compound (D1). This further improves the development solubility.

The photopolymerizable compound (D) preferably further contains a caprolactone-modified polyfunctional compound (D2).

The caprolactone-modified polyfunctional compound (D2) is, for example, trimethylolethane, ditrimethylolethane, trimethylolpropane, ditrimethylolpropane, pentaerythritol, dipentaerythritol, tripentaerythritol, glycerin, diglycerol, trimethylolmelamine and the like. Examples include ε-caprolactone-modified polyfunctional (meth)acrylates obtained by esterifying a hydric alcohol with (meth)acrylic acid and ε-caprolactone. The caprolactone-modified polyfunctional compound (D2) is, for example, a monomer represented by the following general formula (3).

General formula (1)

[In the general formula (1), all six R are groups represented by the following formula (2), or 1 to 5 of the six R are groups represented by the following formula (2), The residue is a group represented by the following formula (3). ]

general formula (2)

[In general formula (2), R ¹ represents a hydrogen atom or a methyl group, m represents the number of 1 or 2, and "*" represents a bond. ]

General formula (3)

[In general formula (3), R ¹ represents a hydrogen atom or a methyl group, and "*" represents a bond. ]

A commercial product of the caprolactone-modified polyfunctional compound (D2) is, for example, commercially available as KAYARAD DPCA series from Nippon Kayaku Co., Ltd. DPCA-20 (m = 1 in the above general formulas (1) to (3), formula ( DPCA-30 (same formula, m = 1, number of groups represented by formula ( ² ) = 3, R ¹ are all hydrogen atoms. compound), DPCA-60 (same formula, m = 1, number of groups represented by formula (2) = 6, R ¹ are all hydrogen atoms), DPCA-120 (m = 2 in the formula, The number of groups represented by the formula (2) is 6, and all R ¹ are hydrogen atoms). Among these, DPCA-20 and DPCA-30, which are excellent in reactivity, are preferable from the viewpoint of pattern straight lines and water spots.

The content of the caprolactone-modified polyfunctional compound (D2) is preferably 2 to 20% by mass, more preferably 3 to 15% by mass, based on 100% by mass of the non-volatile content of the photosensitive coloring composition. This improves the pattern straight line.

The photopolymerizable compound (D) may contain, in addition to the above, a polymerizable compound having a urethane bond and other photopolymerizable compounds.
A polymerizable compound having a urethane bond is a compound having a polymerizable unsaturated group and a urethane bond. Examples of the polymerizable compound having a urethane bond include (1) a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group with a polyfunctional isocyanate, and (2) a reaction product of an alcohol and a polyfunctional isocyanate. , a polyfunctional urethane acrylate obtained by reacting a (meth)acrylate having a hydroxyl group, and the like.

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

Examples of polyfunctional isocyanates include tolylene diisocyanate, hexamethylene diisocyanate, diphenylmethylene diisocyanate, isophorone diisocyanate, and polyisocyanate.

Other photopolymerizable compounds include, for example, methyl (meth)acrylate, ethyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol. di(meth)acrylate, triethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, phenoxytetraethyleneglycol (meth)acrylate, phenoxyhexaethyleneglycol (meth)acrylate, Trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, isocyanurate EO-modified di(meth)acrylate, isocyanurate EO-modified tri(meth)acrylate, ditrimethylolpropane tetra(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, tricyclodecanyl (meth) acrylate, methylolated melamine (meth) acrylic acid ester, epoxy (meth) acrylate, urethane acrylate, and other acrylic and methacrylic acid esters, (meth) acrylic acid , styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl(meth)acrylamide, N-vinylformamide, acrylonitrile and the like.

A photopolymerizable compound (D) can be used individually or in combination of 2 or more types.

The content of the photopolymerizable compound (D) is preferably 2 to 50% by mass, more preferably 2 to 40% by mass, based on 100% by mass of the non-volatile matter of the photosensitive coloring composition. Curability and developability are further improved when blended in an appropriate amount.

<Photoinitiator (E)>
The photopolymerization initiator (E) is, for example, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropane-1- one, 1-hydroxycyclohexylphenyl ketone, 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, Benzophenone compounds such as acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, or 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone, 2-chlorothioxanthone, 2 - Thioxanthone compounds such as methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, or 2,4-diethylthioxanthone; 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloro methyl)-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; 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2- (O-benzoyloxime)], or oxime esters such as ethanone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-,1-(O-acetyloxime) Compounds; Phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide or diphenyl-2,4,6-trimethylbenzoylphosphine oxide; 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone borate compounds; carbazole compounds; imidazole compounds; or titanocene compounds. Among these, oxime ester compounds are preferred.

(Oxime ester compound)
In oxime ester-based compounds, the absorption of ultraviolet light causes cleavage of the NO bond of the oxime to produce iminyl radicals and alkyloxy radicals. Since these radicals are further decomposed to generate highly active radicals, a pattern can be formed with a small amount of exposure. When the colorant concentration of the photosensitive coloring composition is high, the ultraviolet transmittance of the coating film may be low and the degree of curing of the coating film may be low. However, oxime ester compounds are preferably used because they have high quantum efficiency. be.

Oxime ester compounds are oximes described in JP-A-2007-210991, JP-A-2009-179619, JP-A-2010-037223, JP-A-2010-215575, JP-A-2011-020998, etc. Ester-based photopolymerization initiators can be mentioned.

A photoinitiator (E) can be used individually or in combination of 2 or more types.

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

<Sensitizer>
The photosensitive coloring composition can contain a sensitizer.
Sensitizers include, for example, chalcone derivatives, unsaturated ketones such as dibenzalacetone, 1,2-diketone derivatives such as benzyl and camphorquinone, benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, Xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, polymethine dyes such as 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-acyloxyesters, Acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrenequinone, camphorquinone, ethylanthraquinone, 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. Chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3- Benzoyl-N-ethylcarbazole, 3,6-dibenzoyl-N-ethylcarbazole and the like are more preferred.

A sensitizer can be used alone or in combination of two or more.

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

<Thermosetting compound>
The photosensitive coloring composition can contain a thermosetting compound. The thermosetting compound reacts during post-baking of the filter segment to improve the crosslink density of the coating. As a result, the heat resistance of the filter segment is improved, and pigment aggregation can be suppressed, thereby improving the contrast ratio.

The thermosetting compound may be a low-molecular-weight compound or a high-molecular-weight compound such as a resin.
Thermosetting compounds include, for example, epoxy compounds, oxetane compounds, benzoguanamine compounds, rosin-modified maleic acid compounds, rosin-modified fumaric acid compounds, melamine compounds, urea compounds, and phenolic compounds. Among these, epoxy compounds and oxetane compounds are preferred.

<Thiol chain transfer agent>
The photosensitive coloring composition can contain a chain transfer agent. The chain transfer agent is preferably a thiol chain transfer agent. A thiol-based chain transfer agent, when used in combination with a photopolymerization initiator, generates thiyl radicals that are less likely to be inhibited by oxygen during radical polymerization after photoirradiation, improving the sensitivity of the photosensitive coloring composition.

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

Polyfunctional thiols include, for example, hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate , trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolpropane tris(3-mercaptobutyrate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, tris trimercaptopropionate (2-hydroxyethyl) isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine and the like, preferably ethylene glycol bisthiopropionate, trimethylolpropane tristhiopropionate, pentaerythritol tetrakisthiopropionate, and the like.

A thiol-based chain transfer agent can be used alone or in combination of two or more.

The content of the thiol-based chain transfer agent is preferably 1 to 10% by mass, more preferably 2 to 8% by mass, based on 100% by mass of the nonvolatile matter of the photosensitive coloring composition. When contained in an appropriate amount, the 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 photolithographic exposure, making it easier to obtain a pattern of a desired shape.

Polymerization inhibitors include, for example, 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 and 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, alkylresorcinol compounds such as 4-tert-butylresorcinol, methylhydroquinone, ethylhydroquinone, propylhydroquinone, tert-butylhydroquinone, 2 ,5-di-tert-butylhydroquinone and other alkylhydroquinone compounds; tributylphosphine, trioctylphosphine, tricyclohexylphosphine, triphenylphosphine, tribenzylphosphine and other phosphine compounds; Phosphine oxide compounds, phosphite compounds such as triphenylphosphite and trisnonylphenylphosphite, pyrogallol, phloroglucine and the like.

The content of the polymerization inhibitor is preferably 0.01 to 0.4% by mass based on 100% by mass of non-volatile matter in the photosensitive coloring composition. When contained in an appropriate amount, the linearity of the linear portion of the pattern is improved, making it easier to obtain a favorable pattern shape, and wrinkles on the pattern surface can also be suppressed.

<Ultraviolet absorber>
The photosensitive coloring composition can contain an ultraviolet absorber. Examples of ultraviolet absorbers include benzotriazole compounds, triazine compounds, benzophenone compounds, salicylate compounds, cyanoacrylate compounds, and salicylate compounds. In addition, the ultraviolet absorber may be an oligomer or polymer.

Benzotriazole compounds include, for example, 2-(5methyl-2-hydroxyphenyl)benzotriazole, 2-(2-hydroxy-5-t-butylphenyl)-2H-benzotriazole, 2-[2-hydroxy-3 ,5-bis(α,α-dimethylbenzyl)phenyl]-2H-benzotriazole, 2-(3-tbutyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole, 2-(2′- Hydroxy-5′-t-octylphenyl)benzotriazole, 5% 2-methoxy-1-methylethyl acetate and 95% benzenepropanoic acid, 3-(2H-benzotriazol-2-yl)-(1,1 -dimethylethyl)-4-hydroxy, a mixture of C7-9 side chain and linear alkyl esters, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl) Phenol, 2-(2H-benzotriazol-2-yl)-6-(1-methyl-1-phenylethyl)-4-(1,1,3,3-tetramethylbutyl)phenol, methyl 3-(3 -(2H-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.

Triazine compounds include, for example, 2,4-bis(2,4-dimethylphenyl)-6-(2-hydroxy-4-n-octyloxyphenyl)-1,3,5-triazine, 2-[4, 6-bis(2,4-dimethylphenyl)-1,3,5-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)-glycidate, 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- and tris(2-hydroxy-4-hexyloxy-3-methylphenyl)-1,3,5-triazine.

Benzophenone compounds include, for example, 2,4-di-hydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxybenzophenone-5-sulfonic acid-3 water temperature, 2-hydroxy-4-n- Octoxybenzophenone, 2,2'-di-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 4-dodecyloxy-2-hydroxybenzophenone, 2-hydroxy-4-octade siloxybenzophenone, 2,2'dihydroxy-4,4'-dimethoxybenzophenone, 2,2',4,4'-tetrahydroxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone and the like.

Examples of salicylate compounds include phenyl salicylate, p-octylphenyl salicylate, p-tertbutylphenyl salicylate, and the like.

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

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

<Antioxidant>
The photosensitive coloring composition can contain an antioxidant. The antioxidant prevents the photopolymerization initiator and thermosetting compound contained in the photosensitive coloring composition from yellowing due to oxidation during the thermal process during thermal curing and ITO annealing, and can suppress the decrease in the transmittance of the coating. . Especially when the concentration of the coloring agent in the photosensitive coloring composition is high, the content of the photopolymerizable compound (D) is relatively reduced. is prone to yellowing. Therefore, by including an antioxidant, it is possible to prevent yellowing due to oxidation during the heating process, and to suppress a decrease in the transmittance of the coating.

Antioxidants include, for example, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, sulfur-based antioxidants, and the like. In this specification, the antioxidant is preferably a compound containing no halogen atom.

An antioxidant can be used individually or in combination of 2 or more types.

The content of the antioxidant is preferably 0.5 to 5% by mass based on 100% by mass of non-volatile matter in 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 with respect to the transparent substrate and the drying property of the coating when the coating is formed. Examples of leveling agents include silicone surfactants, fluorosurfactants, nonionic surfactants, cationic surfactants, and anionic surfactants.

A leveling agent can be used individually or in combination of 2 or more types.

The content of the leveling agent is preferably 0.001 to 2.0% by mass, more preferably 0.005 to 1.0% by mass, based on 100% by mass of non-volatile matter in the photosensitive coloring composition. Within this range, the applicability of the photosensitive coloring composition, the pattern adhesion, and the transmittance balance are further improved.

<Storage stabilizer>
The photosensitive coloring composition can contain storage stabilizers to stabilize the viscosity of the composition over time. Storage stabilizers include, for example, quaternary ammonium chlorides such as benzyltrimethyl chloride and diethylhydroxyamine; organic acids such as lactic acid and oxalic acid and their methyl ethers; phosphine, phosphite and the like.

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

<Adhesion improver>
The photosensitive coloring composition can contain an adhesion improver. This further improves the adhesion between the coating and the substrate. In addition, it becomes easier to form a narrow pattern by photolithography. Adhesion improvers include, for example, silane coupling agents.

Examples of silane coupling agents include vinylsilanes such as vinyltrimethoxysilane and vinyltriethoxysilane, 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, (Meth)acrylsilanes such as 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane , 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane and other epoxysilanes, N-2-(aminoethyl)-3-aminopropyl methyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-triethoxysilyl-N-(1,3- dimethyl-butylidene)propylamine, N-phenyl-3-aminopropyltrimethoxysilane, aminosilanes such as hydrochloride of N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane, 3-mercaptopropyl mercaptos such as methyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; styryls such as p-styryltrimethoxysilane; ureides such as 3-ureidopropyltriethoxysilane; Examples include sulfides and isocyanates such as 3-isocyanatopropyltriethoxysilane.

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

<Method for producing photosensitive composition>
The photosensitive coloring composition is subjected to dispersion treatment using, for example, an organic pigment (A), a dispersant (B), a solvent, and the like to prepare a pigment dispersion. The organic pigment can be dispersed more finely by using a dispersing aid such as a dye derivative in the dispersing treatment, and the dispersing treatment may not be required when the organic pigment is highly soluble in a solvent. When two or more kinds of organic pigments (A) are used in combination, the pigment dispersion may use pigments separately or may use a plurality of pigments in combination.
Next, the pigment dispersion, the alkali-soluble resin (C), the photopolymerizable compound (D), and the photopolymerization initiator (E) are blended and mixed with stirring to prepare a photosensitive coloring composition. Needless to say, the timing of blending each material is arbitrary.

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

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

Solvents include, for example, ester solvents (solvents containing -COO- in the molecule but not containing -O-), ether solvents (solvents containing -O- in the molecule but not containing -COO-), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule but not -COO-), alcohol solvents (containing OH in the molecule, -O -, -CO- and -COO--free solvents), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide and the like. Among these, a solvent having a boiling point of 120° C. or more and 180° C. or less at 1 atm is preferable in terms of coating properties and drying properties. For example, 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 more preferred, and propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate and the like are even more preferred.

A solvent can be used individually or in mixture of 2 or more types.

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

<Color filter>
The color filter of this specification comprises a base material (also referred to as a substrate or a transparent substrate) and a filter segment formed from a photosensitive coloring composition.
The color filter has a red filter segment, a green filter segment, and a blue filter segment in which the type of organic pigment (A) used is appropriately selected. Also, the color filter can further have a magenta color filter segment, a cyan color filter segment, and a yellow color filter segment. A reflective substrate can be used instead of the transparent substrate. Examples of transparent substrates include glass substrates such as soda lime glass, low-alkali borosilicate glass, and alkali-free aluminoborosilicate glass, and resin substrates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate. Further, a transparent electrode made of indium oxide, tin oxide, or the like may be formed on the surface of the transparent substrate for driving the liquid crystal after panelization.
Examples of the reflective substrate include a substrate using an aluminum electrode or a metal thin film as a reflective surface. The color filter herein is made using the photosensitive coloring composition of this specification for at least one of the plurality of color filter segments.

<Manufacturing method of color filter>
A color filter is preferably formed by first forming a black matrix on a substrate and then forming filter segments. In addition, the black matrix can be formed after thin film transistors (TFTs) are formed on the substrate in advance.
The black matrix includes, for example, a multilayer film of chromium or chromium/chromium oxide, an inorganic film such as titanium nitride, or a resin film in which a light shielding agent is dispersed.

The filter segment can be formed by, for example, a photolithography method or the like. A photolithography method is preferable because a highly accurate color filter can be manufactured. The photolithographic method is described below.

In the photolithography method, for example, a photosensitive coloring composition containing a coloring agent of a certain tone is applied onto a transparent substrate so that the dry film thickness is about 0.2 to 5 μm to form a film. The obtained coating (hereinafter referred to as the first coating) is exposed (light irradiation) through a mask having a predetermined pattern. Next, the film is developed by immersing it in a solvent or an alkaline developer or by spraying the developer to remove uncured portions to obtain a desired pattern. A color filter having filter segments of each color can be produced by performing this step in the same manner using a photosensitive coloring composition having a colorant of another color tone. Also, a second coating (oxygen blocking film) can be formed on the first coating before exposure using polyvinyl alcohol or a water-soluble acrylic resin. As a result, the first film does not come into contact with oxygen, thereby further improving the exposure sensitivity. Also, the color filters can be heated to cure uncured photopolymerizable compounds in the filter segments.

Coating devices include, for example, spray coating, spin coating, slit coating, and roll coating. A drying process can be performed in the case of coating. Examples of the drying device include hot air ovens, infrared heaters, and the like.

Examples of the developer include inorganic alkalis such as sodium carbonate and sodium hydroxide; and organic alkalis such as dimethylbenzylamine and triethanolamine. Also, the developer can contain an antifoaming agent and a surfactant.

The color filter of the present invention is laminated with a counter substrate using a sealing agent, liquid crystal is injected from an injection port provided in the sealing portion, the injection port is sealed, and if necessary, a polarizing film or a retardation film is attached to the substrate. A color liquid crystal display device is manufactured by laminating the film to the outside of the film. This color liquid crystal display device has Twisted Nematic (TN), Super Twisted Nematic (STN), In-Plane Switching (IPS), Vertically Aligned (VA), Optically Convened Bend (OCB). ) can be used in a liquid crystal display mode in which coloration is performed using a color filter.

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

<Liquid crystal display device>
The image display device of this specification includes a color filter. The image display device preferably further includes a light source. A liquid crystal display device will be described below as an example of the image display device. Cold cathode fluorescent lamps (CCFLs) and white LEDs are examples of light sources for liquid crystal display devices. Among these, it is preferable to use a white LED in terms of widening the reproduction range of red. FIG. 1 is a schematic cross-sectional view of a liquid crystal display device 10 having a color filter of the present invention. The device 10 shown in FIG. 1 comprises a pair of transparent substrates 11 and 21 spaced and opposed to each other, with a liquid crystal LC 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). 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 ITO, for example, is formed thereon. An alignment layer 14 is provided on the transparent electrode layer 13 . A polarizing plate 15 is formed on the outer surface of the transparent substrate 11 .

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 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 filters 22, and a transparent electrode layer 23 made of, for example, ITO is formed thereon. is provided.

A polarizing plate 25 is formed on the outer surface of the transparent substrate 21 . 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 phosphor is contained in a resin package of a blue LED. 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 of 600 nm to 650 nm, and has a wavelength The ratio (I4/I3) of the emission intensity I3 at λ3 to the emission intensity I4 at wavelength λ4 is 0.2 or more and 0.4 or less, and the ratio of the emission intensity I3 at wavelength λ3 to the emission intensity I5 at wavelength λ5 (I5/I3 ) has a spectral characteristic of 0.1 to 1.3, and a wavelength (λ1) at which the emission intensity is maximized in the range of 430 nm to 485 nm, and the range of 530 nm to 580 nm has a second emission intensity peak wavelength (λ2) within, and the ratio (I2/I1) of the emission intensity I1 at the wavelength λ1 to the emission intensity I2 at the wavelength λ2 is 0.2 or more and 0.7 or less A white LED light source (LED2) with a is preferred.

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

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

The image display device of the present specification can be used for solid-state imaging devices, organic EL display devices, quantum dot display devices, electronic paper, head-mounted displays, etc., in addition to liquid crystal display devices.

The present invention will be described in detail below based on examples. In the examples, "part" is "mass part" and "%" is "mass%". The compounding amounts in the table are parts by mass unless otherwise specified. In addition, the present invention is not limited to the examples.

First, methods for measuring the weight average molecular weight of the resin and the acid value of the resin will be described.

(Molecular weight of resin)
The number average molecular weight (Mn) and weight average molecular weight (Mw) of the resin were measured by gel permeation chromatography (GPC) equipped with an RI detector. Apparatus: HLC-8220GPC (manufactured by Tosoh Corporation) is used, two separation columns are connected in series, and "TSK-GEL SUPER HZM-N" is used as both packing materials, and the oven temperature is 40 ° C. , a tetrahydrofuran (THF) solution was used as an eluent, and the measurement was performed at a flow rate of 0.35 ml/min. The sample was dissolved in a solvent consisting of 1 wt % of the above eluent and injected in 20 microliters. 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 and stir to dissolve uniformly. (manufactured) to measure the acid value (mgKOH/g) of the resin solution. Then, the acid value per nonvolatile content of the resin was calculated from the acid value of the resin solution and the concentration of the nonvolatile content of the resin solution.

(Production of finely divided pigments (A-1) to (A-5))
Micronized pigments (A-1) to (A-5) in Table 1 were prepared according to the examples of JP-A-2017-111398.

(Refined pigment (A-6))
C. I. 100 parts of Pigment Green 58 (“FASTGEN GREEN A110” manufactured by DIC), 1200 parts of sodium chloride and 120 parts of diethylene glycol were charged in a 1-gallon stainless steel kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 6 hours. This kneaded product is put into 3000 parts of hot water and stirred for 1 hour while heating to 70° C. to form a slurry, which is repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol. Thus, 97 parts of a modified pigment (A-6) was obtained.

(Refined pigment (A-7))
A 300 mL flask was charged with 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 74 parts of bromine. The temperature was raised to 130° C. over 40 hours, the mixture was taken out into water, and a crude green pigment was obtained by coating with filtration. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol and 1.8 parts of xylene were placed in a 1 L twin-arm kneader and kneaded at 100° C. for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80° C., stirred for 1 hour, filtered, washed with hot water, dried and coated by pulverization to obtain a finely divided phthalocyanine pigment (A-7). The resulting finely divided pigment (A-7) has an average number of halogen atoms per molecule of 13.97, of which an average number of bromine atoms is 11.46, according to color fluorescence X-ray analysis by ZSX100E manufactured by Rigaku Corporation. and a halogenated zinc phthalocyanine pigment having an average number of chlorine atoms of 2.51.

(Refined pigment (A-8))
A 300 mL flask was charged with 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 59 parts of bromine. The temperature was raised to 130° C. over 40 hours, the mixture was taken out into water, and a crude green pigment was obtained by coating with filtration. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol and 1.8 parts of xylene were placed in a 1 L twin-arm kneader and kneaded at 100° C. for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80° C., stirred for 1 hour, filtered, washed with hot water, dried and coated by pulverization to obtain a finely divided pigment (A-8). The finely divided phthalocyanine pigment (A-8) thus obtained had an average number of halogen atoms per molecule of 12.71, of which the average number of bromine atoms was 10.22 and the number of chlorine atoms was determined by X-ray fluorescent analysis. was 2.49 on average.

(Refined pigment (A-9))
A 300 mL flask was charged with 91 parts of sulfuryl chloride, 109 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 44 parts of bromine. The temperature was raised to 130° C. over 40 hours, the mixture was taken out into water, and a crude green pigment was obtained by coating with filtration. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol and 1.8 parts of xylene were placed in a 1 L twin-arm kneader and kneaded at 100° C. for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80° C., stirred for 1 hour, filtered, washed with hot water, dried and coated by pulverization to obtain a finely divided pigment (A-9). The finely divided phthalocyanine pigment (A-9) thus obtained had an average number of halogen atoms per molecule of 11.98, of which the average number of bromine atoms was 9.00 and the number of chlorine atoms was determined by X-ray fluorescent analysis. was 2.98 on average.

(Refined pigment (A-10))
A 300 mL flask was charged with 109 parts of sulfuryl chloride, 131 parts of aluminum chloride, 18 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 52 parts of bromine. The temperature was raised to 130° C. over 40 hours, the mixture was taken out into water, and a crude green pigment was obtained by coating with filtration. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol and 1.8 parts of xylene were placed in a 1 L twin-arm kneader and kneaded at 100° C. for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80° C., stirred for 1 hour, filtered, washed with hot water, dried and coated by pulverization to obtain a finely divided pigment (A-10). The finely divided phthalocyanine pigment (A-10) thus obtained had an average number of halogen atoms per molecule of 12.69, an average number of bromine atoms of which was 8.54, and an average number of chlorine atoms of 8.54. was a halogenated zinc phthalocyanine pigment with an average of 4.16.

(Refined pigment (A-11))
A 300 mL flask was charged with 91 parts of sulfuryl chloride, 72 parts of aluminum chloride, 15 parts of sodium chloride, 30 parts of zinc phthalocyanine, and 29 parts of bromine. The temperature was raised to 130° C. over 40 hours, the mixture was taken out into water, and a crude green pigment was obtained by coating with filtration. 20 parts of the obtained green crude pigment, 140 parts of pulverized sodium chloride, 32 parts of diethylene glycol and 1.8 parts of xylene were placed in a 1 L twin-arm kneader and kneaded at 100° C. for 6 hours. After kneading, the mixture was taken out into 2 kg of water at 80° C., stirred for 1 hour, filtered, washed with hot water, dried and coated by pulverization to obtain a finely divided pigment (A-11). The finely divided phthalocyanine pigment (A-11) thus obtained had an average number of halogen atoms of 8.88 per molecule, including an average number of bromine atoms of 6.90 and a number of chlorine atoms of 6.90. was a halogenated zinc phthalocyanine pigment with an average of 1.98.

(Refined pigment (A-12))
C. I. 500 parts of Pigment Green 36 ("Lionol Green 6YK" manufactured by Toyocolor 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) and kneaded at 120° C. for 4 hours. Next, this kneaded product is put into 5 liters of hot water, stirred for 1 hour while heating to 70° C. to form a slurry, repeatedly filtered and washed with water to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a day and night. to obtain 490 parts of finely divided pigment (A-12).

(Refined pigment (A-13))
C. I. Pigment Green 36 with C.I. I. Pigment Green 7 ("Lionol Green YS-07" manufactured by Toyocolor Co., Ltd.) was used in the same manner as for finely divided pigment (A-12), to obtain 490 parts of finely divided pigment (A-13). .

(Refined pigment (A-14))
C. I. Pigment Red 254 ("Irgafor Red B-CF" manufactured by BASF Japan) 100 parts, 1000 parts of crushed salt, and 120 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and heated at 70 ° C. for 8 hours. Kneaded. This mixture is poured into 2000 parts of warm water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent, and then heated at 80°C for 24 hours. After drying, a finely divided pigment (A-14) was obtained.

(Refined pigments (A-15 to 22))
The diketopyrrolopyrrole-based red pigments (a-15 to a-22) shown in Table 2 prepared according to the examples of JP-A-2017-138417 are finely divided as follows, and the finely divided pigments (A-15 to A-22) was obtained.

(Refined pigment (A-15))
100 parts of diketopyrrolopyrrole red pigment (a-15), 1000 parts of sodium chloride, and 120 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 60° C. for 10 hours. Next, the kneaded mixture is put into hot water, stirred for 1 hour while heating to about 80°C to form a slurry, filtered and washed with water to remove salt and diethylene glycol, dried at 80°C for a day and night, and pulverized. By doing so, a finely divided pigment (A-15) was obtained.

(Refined pigments (A-16 to 22))
Except for changing the diketopyrrolopyrrole red pigment (a-15) to the pigment shown in Table 2, the micronization was performed in the same manner as the micronized pigment (A-15), and the micronized pigments (A-16 to A -22) was obtained.

(Refined pigments (A-23 to A-45))
The azo pigments shown in Table 3 produced according to the examples of Japanese Patent No. 6368844 were micronized as follows to obtain micronized pigments (A-23 to A-45).

(Refined pigment (A-23))
80 parts of azo pigment (a-23), 800 parts of sodium chloride, and 90 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho), kneaded at 60° C. for 6 hours, and subjected to salt milling. The resulting kneaded product was poured into 3 liters of hot water, stirred for 1 hour while heating to 70°C to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80°C for a day and night. , to obtain a finely divided pigment (A-23).

(Refined pigments (A-24 to A-45))
Finely divided pigment (A -24 to A-45).

(Refined pigment (A-46))
anthraquinone red pigment C.I. I. Pigment Red 177 ("Sinilex Red SR3C" manufactured by Sinic Co.): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 120 ° C. for 8 hours. did. Next, this kneaded product is put into 5 liters of hot water, stirred for 1 hour while heating to 70° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a day and night. to obtain a finely divided pigment (A-46).

(Refined pigment (A-47))
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 is poured into 3 liters of hot water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which is filtered and washed repeatedly to remove sodium chloride and the solvent. After drying for one day at ℃, a finely divided pigment (A-47) was obtained.

(Refined pigment (A-48))
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 stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 5 hours. . This mixture is poured into 4000 parts of hot water, heated to about 80°C and stirred with a high-speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent, then heated at 80°C for 24 hours. After drying, a finely divided pigment (A-48) was obtained.

(Refined pigment (A-49))
C. I. 100 parts of Pigment Blue 15:6 ("Lionol Blue ES" manufactured by Toyocolor Co., Ltd.), 1000 parts of pulverized salt, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 50° C. for 12 hours. . This mixture is put into 3000 parts of warm water, heated to about 70°C and stirred with a high speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent, then heated to 80°C for 24 hours. After drying, a finely divided pigment (A-49) was obtained.

(Refined pigment (A-50))
C. I. Pigment Yellow 138 (PY138) (BASF Japan Co., Ltd. "Pariotol Yellow K0960-HD") 100 parts, sodium chloride 700 parts, and diethylene glycol 180 parts were charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho) and heated at 80 ° C. Kneaded for 6 hours. This mixture is poured into 2000 parts of hot water and stirred for 1 hour while heating to 80°C to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent. A-50) was obtained.

(Finely divided yellow pigments (A-51) to (A-53))
Finely divided quinophthalone pigments (A-51) to (A-53) shown in Table 4 were prepared according to the examples of JP-A-2012-226110. Its structure is shown below.

(Refined pigment (A-54))
isoindoline yellow pigment C.I. I. 100 parts of pigment yellow 139 (“Irgafor Yellow 2R-CF” manufactured by BASF Japan), 1600 parts of sodium chloride, and 190 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader and kneaded at 60° C. for 10 hours. Next, this mixture is poured into 3 liters of hot water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which is filtered and washed repeatedly to remove sodium chloride and the solvent. C. for one day to obtain a finely divided pigment (A-54).

(Refined pigment (A-55))
Metal complex yellow pigment (CI pigment yellow 150, Lanxess "Yellow Pigment E4GN") 100 parts, 1600 parts of sodium chloride, and 190 parts of diethylene glycol are charged into a stainless steel 1 gallon kneader (manufactured by Inoue Seisakusho), The mixture was kneaded at 60°C for 10 hours. Next, this mixture is poured into 3 liters of hot water, heated to about 80° C. and stirred with a high-speed mixer for about 1 hour to form a slurry, which is filtered and washed repeatedly to remove sodium chloride and the solvent. C. for one day to obtain a finely divided pigment (A-55).

(Refined pigment (A-56))
yellow pigment C.I. I. Pigment Yellow 185 (“Pariotol Yellow D1155” manufactured by Ciba Japan): 500 parts, sodium chloride: 500 parts, and diethylene glycol: 250 parts were placed in a stainless steel 1-gallon kneader and kneaded at 120° C. for 8 hours. Next, this kneaded product is put into 5 liters of hot water, stirred for 1 hour while heating to 70° C. to form a slurry, filtered and washed repeatedly to remove sodium chloride and diethylene glycol, and then dried at 80° C. for a day and night. , to obtain a finely divided pigment (A-56).

(Refined pigment (A-57))
300 parts of dioxazine-based purple pigment PV23 (“Rionogen Violet RL” manufactured by Toyo Ink Mfg. Co., Ltd.) was put into 3000 parts of 96% sulfuric acid, stirred for 1 hour, and poured into water at 5°C. After stirring for 1 hour, the mixture was filtered, washed with warm water until the washing liquid became neutral, and dried at 70°C. 120 parts of the acid pasting-treated pigment, 5 parts of the pigment derivative (Compound 4), 1500 parts of pulverized salt, and 100 parts of diethylene glycol were placed in a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho) and kneaded at 70° C. for 20 hours. did. This mixture is poured into 5000 parts of warm water, heated to about 70°C and stirred with a high-speed mixer for about 1 hour to form a slurry, which is repeatedly filtered and washed with water to remove salt and solvent, then heated to 80°C for 24 hours. After drying, a finely divided pigment (A-57) was obtained.

(Dye solution (a-1 to a-3)
(Resin 1 having a cationic group in the side chain)
A four-necked separable flask equipped with a thermometer, a stirrer, a distillation tube and a condenser was charged with 67.3 parts of methyl ethyl ketone, and the temperature was raised to 75° C. under a nitrogen stream. Separately, 34.0 parts of methyl methacrylate, 28.0 parts of n-butyl methacrylate, 28.0 parts of 2-ethylhexyl methacrylate, 10.0 parts of dimethylaminoethyl methacrylate, 2,2'-azobis(2,4-dimethylvaleronitrile ) and 25.1 parts of methyl ethyl ketone were uniformly stirred, charged into a dropping funnel, attached to a four-necked separable flask, and added dropwise over 2 hours. After 2 hours from the completion of dropping, sampling was performed and it was confirmed that the polymerization yield was 98% or more from the non-volatile matter. In addition, the weight average molecular weight (Mw) was 6,830. It was then cooled to 50°C. Next, 3.2 parts of methyl chloride and 22.0 parts of ethanol were added, and the mixture was reacted at 50°C for 2 hours, then heated to 80°C over 1 hour, and further reacted for 2 hours to complete the reaction. . Thus, Resin 1 having a cationic group in a side chain containing 47% by mass of ammonium group as a resin component was obtained. The ammonium salt value of the obtained resin was 34 mgKOH/g.

(Dye 1)
To 2000 parts of water was added 30 parts of the resin 1 having a cationic group on the side chain as calculated as the non-volatile content, and the mixture was sufficiently stirred and mixed, and then heated to 60°C. On the other hand, 10 parts of C.I. I. An aqueous solution was prepared by dissolving Acid Red 52, and was added dropwise to the previous resin solution. After dropping, the mixture was stirred at 60° C. for 120 minutes to sufficiently react. To confirm the end point of the reaction, the reaction solution was added dropwise to a filter paper, and the point at which no bleeding occurred was regarded as the end point, and it was determined that a salt-forming compound was obtained. After allowing to cool to room temperature while stirring, suction filtration is performed, and after washing with water, salt-forming compounds remaining on the filter paper are dried by removing moisture with a drier. I. Dye 1 was obtained as a salt forming compound of Acid Red 52 and Resin 1 having a cationic group in the side chain. At this time, C.I. I. The content of the active coloring component derived from Acid Red 52 was 25% by mass.

(Dye 2)
C. I. Add Acid Red 52 to C.I. I. Dye 1 was prepared in the same manner as in Dye 1, except that C.I. Acid Red 289 was used. I. Dye 2 was obtained as a salt-forming compound of Acid Red 289 and Resin 1 having a cationic group in the side chain. At this time, C.I. I. The content of the active pigment component derived from Acid Red 289 was 27% by mass.

(Dye 3)
C.I. was placed in a 1 L stainless steel reaction vessel with a condenser under a nitrogen atmosphere. I. 5.0 parts of Basic Violet 10 (BV10: manufactured by Taoka Chemical Co., Ltd.: Rodamine B) and 1.6 parts of hydroxyethyl methacrylate (HEMA) are 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 resulting dichloromethane solution was washed with water, dried under reduced pressure, and purified with a silica gel column to obtain Dye 3.

(Production of dye solution (a-1))
The following mixture was uniformly stirred and mixed, and filtered through a filter with a pore size of 5.0 μm to prepare a coloring composition (dye solution (a-1)).
Coloring agent (dye 1) 12.5 parts Propylene glycol monomethyl ether acetate (hereinafter referred to as PGMAc)
88.5 parts

(Production of dye solutions (a-2) and (a-3))
Dye solutions (a-2) and (a-3) were prepared using Dye 2 and Dye 3 in the same manner as Dye solution (a-1).

(Dye derivative (b))
Table 5 shows the structure of each dye derivative used.

(Production of dispersant (B) solution)
10 parts of methacrylic acid, 100 parts of methyl methacrylate, 70 parts of i-butyl methacrylate, 20 parts of benzyl methacrylate and 50 parts of PGMAc were introduced into a reaction vessel equipped with a gas inlet tube, a temperature control, a condenser and a stirrer, and the atmosphere was purged with nitrogen gas. The inside of the reaction vessel was heated to 50° C. with stirring, and 12 parts of 3-mercapto-1,2-propanediol was added. The temperature was raised to 90° C., and the mixture was reacted for 7 hours while adding a solution of 0.1 part of 2,2′-azobisisobutyronitrile to 90 parts of PGMAc. It was confirmed by measuring the non-volatile content that 95% had reacted. 19 parts of pyromellitic anhydride, 50 parts of PGMAc, 50 parts of cyclohexanone, and 0.4 parts 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 is half-esterified by acid value measurement, the reaction is terminated, and PGMAc is added to dilute so that the nonvolatile content is 30% by nonvolatile content measurement, and the acid value is 70 mgKOH / g. , an acidic resin-type dispersant (B) solution having a weight average molecular weight of 8,500 was obtained.

<Production of binder resin (C1-M: resin having no polymerizable unsaturated group) mixture>
(Preparation of binder resin (C1-1) liquid)
196 parts of propylene glycol monomethyl ether acetate was charged into a reaction vessel equipped with a separable 4-necked flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, a dropping tube and a stirring device, heated to 80°C, and the inside of the reaction vessel was replaced with nitrogen. After that, from the dropping tube, 37.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, paracumylphenol ethylene oxide modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.) A mixture of 20.7 parts and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After completion of dropping, the reaction was continued for 3 more hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. A binder resin (C1-1) liquid was prepared by adding acetate. The weight average molecular weight (Mw) was 26,000.

(Preparation of binder resin (C1-2) liquid)
A flask equipped with a stirrer, a thermometer, a reflux condenser, a dropping funnel and a nitrogen inlet tube was filled with a nitrogen atmosphere, 210 parts of propylene glycol monomethyl ether acetate was added, and the temperature was raised to 100°C while stirring. Then, 106 parts of benzyl methacrylate, 22 parts of acrylic acid and 22 parts of dicyclopentanyl methacrylate (FA-513M manufactured by Hitachi Chemical Co., Ltd.) are dissolved in 215 parts of propylene glycol monomethyl ether acetate, and further 2,2'-azobisisobutyl A solution prepared by dissolving 3.6 parts of lonitrile was dropped into the flask, and the mixture was stirred at 100° C. for 5 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 parts of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. A binder resin was prepared by adding acetate to obtain a resin (C1-2) solution having a weight average molecular weight (Mw) of 10,000.

(Preparation of binder resin (C1-M) liquid)
Equal amounts of binder resin (C1-1) liquid and binder resin (C1-2) liquid were mixed and stirred to prepare a binder resin (C1-M) mixed liquid.

<Production of alkali-soluble resin (C)>
(Preparation of alkali-soluble resin (C-1) solution)
A separable 4-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirring device was charged with 370 parts of cyclohexanone, heated to 80°C, and after replacing the inside of the flask with nitrogen, 32.7 parts of dicyclopentanyl methacrylate which is a cyclic alicyclic monomer unit (c1), 25.7 parts of benzyl methacrylate which is an aromatic-containing monomer unit (c2), 41.5 parts of glycidyl methacrylate, and A mixture of 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, then a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container was replaced with air, and 0.5 part of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 21.1 parts of acrylic acid; and the reaction was continued at 120° C. for 6 hours until the non-volatile acid value reached 0.5, and the reaction was terminated to obtain an acrylic resin solution. Further, 37.3 parts of tetrahydrophthalic anhydride (84% of the hydroxyl groups generated in this reaction) and 0.5 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. Acetate was added to obtain an alkali-soluble resin (C-1) solution having a weight average molecular weight (Mw) of 18,000. In the resin, the molar ratio (c1)/(c2) was 1.0. Moreover, the content of the aromatic-containing monomer unit (c2) was 25.0 mol % in all the monomer units constituting the main chain.

(Preparation of alkali-soluble resin (C-2) solution)
A separable 4-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirring device was charged with 370 parts of cyclohexanone, heated to 80°C, and after replacing the inside of the flask with nitrogen, 52.0 parts of dicyclopentanyl methacrylate which is a cyclic alicyclic monomer unit (c1), 8.4 parts of benzyl methacrylate which is an aromatic-containing monomer unit (c2)), 39.7 parts of glycidyl methacrylate, and 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, then a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container is replaced with air, and 20.1 parts of acrylic acid (100% of the glycidyl groups generated in this reaction), 0.5 parts of trisdimethylaminophenol and 0.1 parts of hydroquinone are added to the above container. Then, the reaction was continued at 120° C. for 6 hours until the non-volatile content acid value reached 0.5, and the reaction was terminated to obtain a solution of an acrylic resin. Further, 35.7 parts of tetrahydrophthalic anhydride (84% of the hydroxyl groups generated in this reaction)] and 0.5 part of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. An alkali-soluble resin (C-2) solution was prepared by adding acetate. The weight average molecular weight (Mw) was 18,500. In the resin, the molar ratio (c1)/(c2) was 4.9. In addition, the content of the aromatic-containing monomer unit (c2) was 8.5 mol% in all the monomer units constituting the main chain.

(Preparation of alkali-soluble resin (C-3) solution)
A separable 4-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirring device was charged with 370 parts of cyclohexanone, heated to 80°C, and after replacing the inside of the flask with nitrogen, 16.3 parts of dicyclopentanyl methacrylate which is a cyclic alicyclic monomer unit (c1), 40.6 parts of benzyl methacrylate which is an aromatic-containing monomer unit (c2), 43.1 parts of glycidyl methacrylate, and A mixture of 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, then a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container was replaced with air, and 21.9 parts of acrylic acid (100% of the glycidyl groups generated in this reaction), 0.5 parts of trisdimethylaminophenol and 0.1 parts of hydroquinone were charged into the above container. Then, the reaction was continued at 120° C. for 6 hours until the non-volatile content acid value reached 0.5, and the reaction was terminated to obtain a solution of an acrylic resin. Further, 38.7 parts of tetrahydrophthalic anhydride (84% of the hydroxyl groups generated in this reaction) and 0.5 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. An alkali-soluble resin (C-3) solution was prepared by adding acetate. The weight average molecular weight (Mw) was 19,000. In the resin, the molar ratio (c1)/(c2) was 0.3. In addition, the content of the aromatic-containing monomer unit (c2) was 38.0 mol% in all the monomer units constituting the main chain.

(Preparation of alkali-soluble resin (C0) solution)
A separable 4-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirring device was charged with 370 parts of cyclohexanone, heated to 80°C, and after replacing the inside of the flask with nitrogen, 53.6 parts of dicyclopentanyl methacrylate which is a cyclic alicyclic monomer unit (c1), 6.9 parts of benzyl methacrylate which is an aromatic-containing monomer unit (c2), 39.5 parts of glycidyl methacrylate, and A mixture of 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, then a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container was changed to air exchange, and 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 20.1 parts of acrylic acid (100% of glycidyl groups) in the container, and the mixture was heated at 120°C. The reaction was continued for 6 hours until the acid value of the non-volatile matter reached 0.5, and the reaction was terminated to obtain a solution of an acrylic resin. Further, 35.5 parts of tetrahydrophthalic anhydride (84% of the hydroxyl groups generated in this reaction) and 0.5 part of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain an acrylic resin solution. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180 ° C. for 20 minutes to measure the nonvolatile content. An alkali-soluble resin (C0) solution was prepared by adding acetate. The weight average molecular weight (Mw) was 18,700. In the resin, the molar ratio (c1)/(c2) was 6.0. In addition, the content of the aromatic-containing monomer unit (c2) was 7.0 mol % in all the monomer units constituting the main chain.

(Preparation of alkali-soluble resin (C-4) solution)
A separable 4-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirring device was charged with 370 parts of cyclohexanone, heated to 80°C, and after replacing the inside of the flask with nitrogen, 36.5 parts of dicyclopentanyl methacrylate which is a cyclic alicyclic monomer unit (c1), 5.7 parts of benzyl methacrylate which is an aromatic-containing monomer unit (c2), 57.8 parts of glycidyl methacrylate, and A mixture of 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, then a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container was changed to air exchange, and 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 29.3 parts of acrylic acid (100% of glycidyl groups) in the container, and the mixture was heated at 120°C. The reaction was continued for 6 hours until the acid value of the non-volatile matter reached 0.5, and the reaction was terminated to obtain a solution of an acrylic resin. Further, 52.0 parts of tetrahydrophthalic anhydride (84% of the hydroxyl groups generated in this reaction) and 0.5 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, propylene glycol monomethyl ether acetate was added so that the non-volatile content was 20% by mass to prepare an alkali-soluble resin (C-4) solution having a weight average molecular weight (Mw) of 19,100. In the resin, the molar ratio (c1)/(c2) was 5.0. Moreover, the content of the aromatic-containing monomer unit (c2) was 4.0 mol % in all the monomer units constituting the main chain.

(Preparation of alkali-soluble resin (C-5) solution)
A separable 4-necked flask equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirring device was charged with 370 parts of cyclohexanone, heated to 80°C, and after replacing the inside of the flask with nitrogen, 22.1 parts of dicyclopentanyl methacrylate which is a cyclic alicyclic monomer unit (c1), 40.5 parts of benzyl methacrylate which is an aromatic-containing monomer unit (c2), 37.4 parts of glycidyl methacrylate, and A mixture of 2.0 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours. After the dropwise addition, the mixture was further reacted at 100°C for 3 hours, then a solution obtained by dissolving 1.0 part of azobisisobutyronitrile in 50 parts of cyclohexanone was added, and the reaction was further continued at 100°C for 1 hour. Next, the inside of the container was changed to air exchange, and 0.5 parts of trisdimethylaminophenol and 0.1 part of hydroquinone were added to 19.0 parts of acrylic acid (100% of glycidyl groups), and the mixture was heated at 120°C. The reaction was continued for 6 hours until the acid value of the non-volatile matter reached 0.5, and the reaction was terminated to obtain a solution of an acrylic resin. Further, 33.6 parts of tetrahydrophthalic anhydride (84% of the hydroxyl groups generated in this reaction) and 0.5 parts of triethylamine were added and reacted at 120° C. for 3.5 hours to obtain an acrylic resin solution.
After cooling to room temperature, propylene glycol monomethyl ether acetate was added so that the non-volatile content was 20% by mass to prepare an alkali-soluble resin (C-5) solution having a weight average molecular weight (Mw) of 18,900. In the resin, the molar ratio (c1)/(c2) was 0.4. In addition, the content of the aromatic-containing monomer unit (c2) was 38.9 mol% in all the monomer units constituting the main chain.

<Preparation of colored composition>
(Production of coloring composition)
[Production Example 1]
After stirring and mixing the following mixture uniformly, using zirconia beads with a diameter of 0.5 mm, after dispersing for 3 hours with an Eiger mill (manufactured by Eiger Japan Co., Ltd. "Mini Model M-250 MKII"), the pore size is 5.5 mm. The mixture was filtered through a 0 μm filter to prepare a coloring composition (X-1) having a nonvolatile content of 20% by mass.
Pigment (A) 20.0 parts Dispersant (B: 30% non-volatile solution) 10.0 parts Binder resin (C1-M: 20% non-volatile solution) 15.0 parts Solvent (O) 55.0 parts The solvent (O) is a mixture of the following (O-1) to (O-7) in parts by mass.
(O-1) 20 parts of PGMAc (O-2) 20 parts of cyclohexanone (O-3) 20 parts of ethyl 3-ethoxypropionate (O-4) 10 parts of propylene glycol monomethyl ether (O-5) 10 parts of cyclohexanol acetate (O-6) 10 parts of dipropylene glycol methyl ether acetate (O-7) 10 parts of propylene glycol diacetate

[Production Examples 2 to 62]
(Production of colored composition (X-2 to 62))
Coloring compositions (X-2 to 62) were prepared in the same manner as the coloring composition (X-1) except that the compositions shown in Table 6 were changed.

[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 solution (X-1: non-volatile content 25.0%): 40.0 parts alkali-soluble resin (C) solution (C-1: non-volatile content 20%): 22.0 parts photopolymerizable compound (D) : 3.0 parts Photopolymerization initiator (E): 0.4 parts thermosetting compound solution (G-1: nonvolatile content 40%): 0.5 parts thermosetting compound solution (G-2: nonvolatile content 40 %): 0.5 parts Sensitizer (H): 0.1 parts Leveling agent (I: non-volatile matter 3%): 1.0 parts Thiol-based chain transfer agent (J): 0.4 parts Antioxidant ( K): 0.1 part Polymerization inhibitor (L): 0.05 part Storage stabilizer (M): 0.1 part Ultraviolet absorber (N): 0.1 part Solvent (O): 15.75 parts

[Examples 2 to 117, Comparative Examples 1 to 6]
(Photosensitive coloring composition (Y-2 to Y-117, Y-201 to Y-206))
In the same manner as the photosensitive coloring composition (Y-1), except that the composition shown in Tables 7-1 to 7-4 and the blending amount (parts by mass) were changed, the mixture was stirred until uniform. After mixing, the mixture was filtered through a 1 μm filter to obtain photosensitive coloring compositions (Y-2 to Y-117, Y-201 to Y-206). Note that Examples 116 and 117 in this specification are reference examples.

The contents of each symbol described in Table 7 are as follows.

<Polymerizable compound (D)>
(D-1) a mixture of pentaerythritol triacrylate (having 3 polymerizable unsaturated groups) and pentaerythritol tetraacrylate (having 4 polymerizable unsaturated groups); acid value: 0
[Aronix M306 (manufactured by Toagosei Co., Ltd.)]
(D-2) a mixture of dipentaerythritol pentaacrylate (having 5 polymerizable unsaturated groups) and dipentaerythritol hexaacrylate (having 6 polymerizable unsaturated groups); acid value: 0
[Aronix M402 (manufactured by Toagosei Co., Ltd.)]
<Carboxyl group-containing polyfunctional compound (D1)>
(D1-1) a mixture of succinic acid-modified dipentaerythritol pentaacrylate (having 5 polymerizable unsaturated groups) and dipentaerythritol hexaacrylate (having 6 polymerizable unsaturated groups); acid value: 30
(D1-2) a mixture of succinic acid-modified dipentaerythritol pentaacrylate (having 5 polymerizable unsaturated groups) and dipentaerythritol hexaacrylate (having 6 polymerizable unsaturated groups); acid value: 65
(D1-3) a mixture of succinic acid-modified pentaerythritol triacrylate (having 3 polymerizable unsaturated groups) and pentaerythritol tetraacrylate (having 4 polymerizable unsaturated groups); acid value: 100
<Caprolactone-modified polyfunctional compound (D2)>
(D2-1) caprolactone-modified dipentaerythritol hexaacrylate; acid value: 0, number of polymerizable unsaturated groups: 6
[KAYARAD DPCA-20 (manufactured by Nippon Kayaku Co., Ltd.)]
(D2-2) caprolactone-modified dipentaerythritol hexaacrylate; acid value: 0, number of polymerizable unsaturated groups: 6
[KAYARAD DPCA-30 (manufactured by Nippon Kayaku Co., Ltd.)]
(D2-3) caprolactone-modified dipentaerythritol hexaacrylate; acid value: 0, number of polymerizable unsaturated groups: 6
[KAYARAD DPCA-60 (manufactured by Nippon Kayaku Co., Ltd.)]
(D2-4) caprolactone-modified dipentaerythritol hexaacrylate; acid value: 0, number of polymerizable unsaturated groups: 6
[KAYARAD DPCA-120 (manufactured by Nippon Kayaku Co., Ltd.)]
The above (D2-1) to (D2-4) were mixed in equal amounts to obtain a polymerizable compound (D2).

<Photoinitiator (E)>
(E-1) 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one
[Omnirad 907 (manufactured by IGM Resins)]
(E-2) 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone
[Omnirad 379EG (manufactured by IGM Resins)]
(E-3) 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide
[Omnirad TPO (manufactured by IGM Resins)]
(E-4) 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole
[Biimidazole (manufactured by Kurogane Kasei Co., Ltd.)]
(E-5) p-dimethylaminoacetophenone
[DMA (manufactured by Daiki Fine)]
(E-6) 1,2-octanedione, 1-[4-(phenylthio)phenyl-, 2-(O-benzoyloxime)
[Irgacure OXE01 (manufactured by BASF Japan)]
(E-7) 1-[4-(2-hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propan-1-one
[Omnirad 2959 (manufactured by IGM Resins)]
(E-8) bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide
[Omnirad 819 (manufactured by IGM Resins)]
(E-9) Ethan-1-one, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl], 1-(O-acetyloxime)
[Irgacure OXE02 (manufactured by BASF Japan)]
(E-10) oxime ester compound
[Irgacure OXE03 (manufactured by BASF Japan)]
(E-11) oxime ester compound
[Irgacure OXE04 (manufactured by BASF Japan)]
The above (E-1) to (E-8) were mixed in equal amounts to obtain a photopolymerization initiator (E1).
The above (E-1) to (E-11) were mixed in equal amounts to obtain a photopolymerization initiator (E).

<Thermosetting compound (G)>
・Thermosetting compound (G-1)
(G-1-1) 1,2-epoxy-4-(2-oxiranyl)cyclohexane adduct of 2,2′-bis(hydroxymethyl)-1-butanol
[EHPE-3150 (manufactured by Daicel Corporation)],
(G-1-2) Glycidyl etherified epoxy compound of sorbitol
[Denacol EX611 (manufactured by Nagase ChemteX Corporation)],
(G-1-3) Triglycidyl isocyanurate (G-1-1) to (G-1-3) are mixed in the same amount and diluted with PGMAc to adjust the non-volatile content to 40%, which is thermosetting. This was designated as compound (G-1).
- Thermosetting compound (G-2):
3-ethyl-3-[(3-ethyloxetan-3-yl)methoxymethyl]oxetane
A thermosetting compound (G-2) was obtained by diluting [Aron oxetane OXT-221 (manufactured by Toagosei Co., Ltd.)] with PGMAc to adjust the non-volatile content to 40%.

<Sensitizer (H)>
(H-1) 2,4-diethylthioxanthone [Kayacure DETX-S (manufactured by Nippon Kayaku Co., Ltd.)]
(H-2) 4,4′-bis(diethylamino)benzophenone [CHEMARK DEABP (manufactured by Chemmark Chemical)]
The above (H-1) and (H-2) were mixed in equal amounts to obtain a sensitizer (H).

<Leveling agent (I)>
"BYK-330" manufactured by Big Chemie Co., Ltd. 1 copy,
A mixed solution prepared by dissolving 1 part of "Megafac F-551" manufactured by DIC and 1 part of "EMULGEN 103" manufactured by Kao in 97 parts of PGMAc.

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

<Antioxidant (K)>
(K-1) pentaerythritol tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate (K-2) 3,3′-dioctadecyl thiodipropanoate (K-3) tris[2 ,4-di-(t)-butylphenyl]phosphine (K-4) bis(2,2,6,6-tetramethyl-4-piperidyl) sebacate (K-5) p-octylphenyl salicylate or more, Equal amounts of (K-1) to (K-5) were mixed to obtain an antioxidant (K).

<Polymerization inhibitor (L)>
(L-1) 3-methylcatechol (L-2) methylhydroquinone (L-3) tert-butylhydroquinone and above, (L-1) to (L-3) are mixed in equal amounts, and a polymerization inhibitor is added. (L).

<Storage stabilizer (M)>
(M-1) 2,6-bis(1,1-dimethylethyl)-4-methylphenol ("BHT" manufactured by Honshu Chemical Industry Co., Ltd.)
(M-2) Triphenylphosphine (“TPP” manufactured by Hokko Chemical Industry Co., Ltd.)
The above (M-1) and (M-2) were mixed in equal amounts to obtain a storage stabilizer (M).

<Ultraviolet absorber (N)>
(N-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)]
(N-2) 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol [TINUVIN900 (manufactured by BASF Japan)]
The above (N-1) and (N-2) were mixed in equal amounts to obtain an ultraviolet absorber (N).

<Evaluation of photosensitive coloring composition>
The obtained photosensitive coloring compositions (Y-1 to Y-117, Y-201 to Y-206) were evaluated by the following methods. Table 8 shows the results. The meaning of the evaluation rank is as follows.
◎: Very good, 〇: Good, △: Practical, ×: Not practical

(Development solubility evaluation)
The obtained photosensitive coloring composition is coated on a glass substrate of 100 mm long×100 mm wide and 1.1 mm thick using a spin coater so that the thickness after drying becomes 2.5 μm, and dried under reduced pressure to obtain a substrate. Ta. Next, after holding the obtained substrate on a hot plate heated to 90° C. for 2 minutes, an ultra-high pressure mercury lamp was used to expose the substrate through a photomask having a predetermined stripe pattern at an illumination intensity of 30 mW/cm ² . UV exposure was performed at 50 mJ/cm ² . The filter segment was treated with an alkali containing 0.15% by mass of sodium carbonate, 0.05% by mass of sodium bicarbonate, 0.1% by mass of an anionic surfactant ("Pelex NBL" manufactured by Kao Corporation), and 99.7% by mass of water. Spray development was carried out using the developer, and after 50 seconds, the developer waste was checked to visually confirm whether solids remained. The evaluation was evaluated in the following three stages. : There is no solid in the liquid and the solution is not suspended. : There are no solids, but the whole liquid is suspended. La: Solid precipitates and aggregates.

[Pattern linearity evaluation]
The obtained photosensitive coloring composition is coated on a glass substrate of 100 mm long×100 mm wide and 1.1 mm thick using a spin coater so that the thickness after drying becomes 2.5 μm, and dried under reduced pressure to obtain a substrate. Ta. Next, after holding for 2 minutes on a hot plate heated to 90° C., an ultra-high pressure mercury lamp was used at an illumination intensity of 30 mW/cm ² and an exposure amount of 50 mJ/cm ² through a photomask having a predetermined stripe pattern. UV exposure was performed. The linearity of the pattern at the 100 μm photomask portion of the obtained filter segment was observed and evaluated using an optical microscope. Evaluation criteria are as follows.
○: Good linearity △: Partially poor linearity (slight chipping)
×: Poor linearity

<Water stain>
The obtained photosensitive coloring composition is coated on a glass substrate of 100 mm long×100 mm wide and 1.1 mm thick using a spin coater so that the thickness after drying becomes 2.5 μm, and dried under reduced pressure to obtain a substrate. Ta. Next, after being held on a hot plate heated to 90° C. for 2 minutes, an ultra-high pressure mercury lamp was used at an illumination intensity of 30 mW/cm ² and an exposure amount of 50 mJ/cm ² through a photomask having a predetermined stripe pattern. UV exposure was performed. The coating film after exposure was spray-developed, and the pattern of the 100 μm photomask portion of the filter segment formed after spray-development was observed and evaluated using an optical microscope. The rank of evaluation is as follows.
◎: No water stains ○: Water stains on an area of 1% to less than 10% △: Water stains on an area of 10% to less than 50% ×: Water stains on an area of 50% or more

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 (9)

Contains an organic pigment (A), a dispersant (B), an alkali-soluble resin (C), a photopolymerizable compound (D), and a photopolymerization initiator (E),
The alkali-soluble resin (C) contains a polycyclic alicyclic monomer unit (c1) and an aromatic-containing monomer unit (c2) at a molar ratio of (c1)/(c2) = 5 to 0.3. It is a resin that
The photopolymerizable compound (D) includes a carboxyl group-containing polyfunctional compound (D1) of a compound having 3 polymerizable unsaturated groups ,
The carboxyl group-containing polyfunctional compound (D1), which is a compound having three polymerizable unsaturated groups, is any one of succinic acid-modified pentaerythritol triacrylate, phthalic acid-modified pentaerythritol triacrylate and malonic acid-modified pentaerythritol triacrylate. A photosensitive coloring composition comprising : The photosensitive coloring composition according to claim 1, wherein the mass ratio of the alkali-soluble resin (C) and the carboxyl group-containing polyfunctional compound (D1) is (C)/(D1) = 0.02 to 15. The photosensitive coloring composition according to claim 1 or 2, containing 2 to 38% by weight of the carboxyl group-containing polyfunctional compound (D1) in 100% by weight of the nonvolatile matter of the photosensitive coloring composition. The photosensitive coloring composition according to any one of claims 1 to 3, wherein the photopolymerizable compound (D) contains a caprolactone-modified polyfunctional compound (D2). 4. The alkali-soluble resin (C) according to any one of claims 1 to 4, containing 4 to 35 mol% of aromatic-containing monomer units (c2) in all monomer units constituting the main chain of the alkali-soluble resin (C). Photosensitive coloring composition Alkali-soluble resin (C) is a resin (C1) containing a polymerizable unsaturated group, photosensitive coloring composition according to any one of claims 1 to 5 The acid value of the alkali-soluble resin (C) is an acid value lower than the acid value of the carboxyl group-containing polyfunctional compound (D1), the photosensitive coloring according to any one of claims 1 to 6 . Composition A color filter comprising a substrate and a filter segment formed from the photosensitive coloring composition according to any one of claims 1 to 7 . An image display device comprising the color filter according to claim 8 .